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Full text of "Technology for using sulfate waste in road construction"

TE 
662 
.A3 
no . 

FH WA- 
RD - 
76-31 



Report No. FHWARD- 76-31 



Dept of Transportation 



JUL 29 1976 



TECHNOLOGY FOR USING SULFATE^ 



WASTE IN HIGHWAY CONSTRUCTION 



L. M. Smith and others 




^mo*^ 



December 1975 

Final Report 



This document is available to the public 
through the National Technical Information 
Service, Springfield, Virginia 22161 



Prepared for 

FEDERAL HIGHWAY ADMINISTRATION 

Offices of Research & Development 
Washington, D.C. 20590 



NOTICE 



This document is disseminated under the sponsorship of the Department of 
Transportation in the interest of information exchange. The United States 
Government assumes no liability for its contents or use thereof. 

The contents of this report reflect the views of Gillette Research Insti- 
tute, which is responsible for the facts and the accuracy of the data pre- 
sented herein. The contents do not necessarily reflect the official views 
or policy of the Department of Transportation. This report does not con- 
stitute a standard, specification, or regulation. 

The United States Government does not endorse products or manufacturers. 
Trade or manufacturers' names appear herein only because they are con- 
sidered essential to the object of this document. 



FHWA DISTRIBUTION NOTICE 



This report is being given limited distribution, primarily to research 
audiences, by FHWA transmittal memorandum. 



r\o ■ 



Technical Report Documentation Page 



1. Report No. 

FHWA-RD-76-31 



2. Government Accession No. 



3. Recipient's Catalog No. 



4. Title and Subtitle 

TECHNOLOGY FOR USING SULFATE WASTE IN 
ROAD CONSTRUCTION 



5. Report Date 

December 1975 



6. Performing Organization Code 



8. Performing Organization Report No. 



Author's) L> M# smith, A. Kawam, M. S. Whitcraft, 

H. G. Larew, F. McCormick, and L. C. Rude 



9. Performing Organization Name and Address 

Gillette Research Institute 
1413 Research Boulevard 
Rockville, Maryland 20850 



10. Work Unit No. (TRAIS) 

FCP 34C2-022 



11. Contract or Grant N 



DOT-FH- 11-8122 



12. Sponsoring Agency Name and Address 

U. S. Department of Transportation 
Federal Highway Administration 
Offices of Research and Development 
Washington, D. C. 20590 



13. Type of Report and Period Covered 

Final Report 



14. Sponsoring Agency Code 



15. Supplementary Notes 

FHWA Contract Manager: W. C. Ormsby (HRS-23); Implementation Manager: R.E. Olsen 
H. G. Larew, F. McCormick and L. C. Rude are associated with the Department 
of Civil Engineering, University of Virginia. 



16. Abstract 

Mixtures of fly ash, lime and sulfate waste were examined for their potential 
use in highway construction. Initially, pure calcium sulfate compounds such 
as gypsum were used as the source of sulfate. In most cases, gypsum was 
found to increase the compressive strength of lime- fly ash-water mixtures. 
During this initial phase of the project, variables such as fly ash source, 
form of calcium sulfate, lime type, mixture consistency, curing temperature, 
admixtures and impurities expected in waste sulfates were examined. Also, 
studies of compound development in selected mixtures were performed. 

The second phase of the study was designed to obtain strength-compositional 
relationships for samples prepared with actual waste sulfates. These waste 
sulfates included neutralized acid mine drainage, titangypsum, hydrofluoric 
acid by-product, gas scrubber waste and neutralized steel pickling liquor. 
Results of this phase were used for the selection of mixtures for engineer- 
ing evaluation. These mixtures were examined for compressive and tensile 
strength, freeze/thaw resistance, wet/dry stability, California bearing 
ratio, permeability and leachability . 

Finally, the possibility of preparing aggregate from mixtures containing 
waste sulfate was examined. The aggregate, as well as portland cement con- 
crete and asphaltic concrete prepared with it, was tested using standard 
techniques . 



17. Key Words 

Waste sulfate, Waste utilization, 
Lime, Fly ash, Calcium sulfate, Dura- 
bility test, Synthetic aggregate, 
Compound identification 



18. Distribution Statement 

No restrictions. This document is 
available to the public through 
the National Technical Information 
Service, Springfield, Virginia 22161 



19. Security Classif. (of this report) 

Unclassified 



20. Security Classif. (of this page) 

Unclassified 



21. No. of Pages 

199 



22. Price 



Form DOT F 1700.7 (8-72) 



Reproduction of completed page authorized 



PREFACE 

We gratefully acknowledge the frequent and stimulating discussions and 
consultations with Dr. Delia M. Roy, Department of Materials Sciences, Penn- 
sylvania State University. Her contributions to the morphological and miner- 
alogical examinations carried out during the project were most valuable to 
the successful completion of the work. 

We express our thanks to Clem DeWitt and Bill Magrini, who assisted in 
many phases of the experimental work. 

To the staff of the Materials Division, Federal Highway Administration, 
who participated in this project, especially the contract managers, Dr. W. 
Clayton Ormsby and the late Earl B. Kinter, we express our appreciation. 

We are also indebted to the many, many people who gave freely of their 
time to discuss with us various aspects of waste production and utilization. 
Special mention is made of the companies and organizations that supplied 
samples of their waste sulfate, gypsum and fly ash: Allegheny Power and 
Service Corp., Armco Steel Co., Consolidation Coal Co., E. I. DuPont De 
Nemours and Co., Environmental Protection Agency, Jones and Laughlin Steel 
Co., Kansas Power and Light Co., Louisville Gas and Electric Co., Monongahela 
Power Co., Northern States Power Co., SCM Corp., and U. S. Gypsum Co. 



11 



TABLE OF CONTENTS 

Page 

INTRODUCTION 1 

EXPERIMENTAL PROCEDURES 4 

Materials 4 

Engineering Test Methods 5 

Compaction 5 

Extrusion 5 

Slump determination 6 

Strength specimen preparation 6 

Density determination 8 

Strength measurements 8 

Dimensional changes 8 

Compound identification 9 

EXPERIMENTAL RESULTS 11 

Development of an Optimized Lime-Fly Ash-Calcium Sulfate System 11 

Moisture-density relationship 11 

Full factorial experimental design 11 

Optimizing the lime/sulfate ratio 15 

Optimizing the fly ash/ (lime + sulfate) ratio 16 

Maximizing the sulfate content 18 

Lime type 20 

Use of anhydrous calcium sulfate . 20 

Low temperature curing 21 

Portland cement addition 21 

Admixtures and impurities 23 

Characterization of Reaction Products in Lime-Fly Ash-Calcium 

Sulfate Systems 25 

Use of Waste Sulfates in Lime-Fly Ash-Sulfate-Water Systems . . 33 

Characterization of waste sulfate materials 33 

Strength studies of waste sulfate mixtures 35 

Engineering evaluation 39 

Determination of engineering properties 40 

Durability studies 41 

Leachate analysis 43 



in 



TABLE OF CONTENTS (Continued) 

Page 

Study of Lime-Fly Ash-Sulfate Systems as Aggregate for Portland 

Cement and Bituminous Concrete 44 

Materials and aggregate preparation 45 

Aggregate manufacture and gradation 46 

Aggregate properties 49 

Portland cement concrete mixture studies 52 

Bituminous concrete mixture studies 60 

SUMMARY OF RESULTS 63 

RECOMMENDATIONS FOR FURTHER RESEARCH 65 

APPENDICES 66 

REFERENCES 88 

ILLUSTRATIONS 89 

TABLES 143 



iv 



LIST OF ILLUSTRATIONS 
Figure Page 

1 - Calibration curve for slump cone 89 

2 - Mixture at extrudable consistency 90 

3 - Apparatus for measuring dimensional changes ... 91 

4 - Dry density vs. moisture content using Ft. Martin 

fly ash 92 

5 - Dry density vs. moisture content using Black Dog 

fly ash 93 

6 - Dry density vs. moisture content using Amax fly ash .... 94 

7 - Dry density vs. moisture content using Albright fly ash 

and Hatfield's Ferry fly ash 95 

8 - Unconfined compressive strength at 7, 28, and 91 days for 

mixtures using Ft. Martin fly ash 96 

9 - Unconfined compressive strength at 7, 28, and 91 days for 

mixtures using Black Dog fly ash 97 

10 - Unconfined compressive strength at 7, 28, and 91 days for 

mixtures using Amax fly ash 98 

11 - Unconfined compressive strength at 7, 28, and 91 days for 

mixtures using Albright fly ash 99 

12 - Unconfined compressive strength at 7, 28, and 91 days for 

mixtures using Hatfield's Ferry fly ash 100 

13 - Unconfined compressive strength vs. lime/sulfate for 

Ft. Martin fly ash 101 

14 - Unconfined compressive strength vs. lime/sulfate for 

Amax fly ash 102 

15 - Optimizing the lime/sulfate ratio for an extrudable 

consistency using Ft. Martin fly ash 103 

16 - Optimizing the lime/sulfate ratio for an extrudable 

consistency using Amax fly ash 104 

17 - Optimizing the lime/sulfate ratio for a slump consistency 

using Ft. Martin fly ash 105 

18 - Optimizing the lime/sulfate ratio for a slump consistency 

using Amax fly ash 106 

19 - Unconfined compressive strength at 7 and 28 days at 

varying fly ash/(lime + sulfate) using Ft. Martin 

fly ash 107 



v 



LIST OF ILLUSTRATIONS (cont'd) 
Figure Page 

20 - Unconfined compressive strength at 7 and 28 days at 

varying fly ash/ (lime + sulfate) using Amax fly ash . . 108 

21 - Optimizing the fly ash/ (lime + sulfate) ratio for an 

extrudable consistency using Ft. Martin fly ash .... 109 

22 - Unconfined compressive strength at varying fly ash/ (lime + 

sulfate) for mixtures containing Ft. Martin and 

Amax fly ash at three- inch slump consistency 110 

23 - Variation in strength with gypsum content at 7 and 28 days 

for Amax fly ash Ill 

24 - Variation in strength with gypsum content for Ft. Martin 

fly ash at 7 and 28 days 112 

25 - Scanning electron micrograph (SEM) of Ft. Martin fly ash - 

2000x 113 

26 - SEM of gypsum - 2000x 114 

27 - SEM of calcitic lime - 2000x 115 

28 - X-ray diffraction pattern of standard mixture 116 

29 - SEM of standard mixture - unreacted (2000x) 117 

30 - SEM of standard mixture - 7 days (2000x) . 118 

31 - SEM of standard mixture - 28 days (2000x) 119 

32 - SEM of standard mixture - unreacted (6000x) 120 

33 - SEM of standard mixture - 7 days (6000x) . 121 

34 - SEM of standard mixture - 14 days (6000x) 122 

35 - SEM of standard mixture - 28 days (6000x) 123 

36 - SEM of standard mixture - 91 days (2000x) 124 

37 - SEM of standard mixture - 9 months (1530x) 125 

38 - SEM of calcium sulfite mixture - 91 days (2000x) 126 

39 - SEM of slump consistency mixture - 28 days (604 5x) 127 

40 - SEM of extrudable consistency mixture - 7 months (2000x) . . 128 

41 - X-ray diffraction pattern of extrudable consistency 

mixture - 7 months 129 

42 - SEM of slump consistency mixture (9600x) 130 

43 - Acid mind drainage (W„) samples after three cycles of 

freeze-thaw 131 

44 - Unbrushed samples of scrubber sludge (W fi ) cured for 28 days. 132 

vi 



LIST OF ILLUSTRATIONS (cont'd) 

Figure Page 

45 - Aggregate particle subsequent to soundness test 134 

46 - Aggregate particles after 12 cycles of freeze-thaw 135 

47 - Concrete test specimens showing molding defects 136 

48 - Variation in compressive strength with slump and cement 

factor 137 

49 - Variation in compressive strength with aggregate gradation 

for w/c of 0.51 138 

50 - Variation in compressive strength with aggregate gradation 

for w/c of 0.68 139 

51 - Typical surface cracks on freeze-thaw concrete specimens . . 140 

52 - Freeze-thaw concrete specimens after 103 cycles ...... 141 

53 - Close-up view of interior surface of freeze-thaw concrete 

specimen 142 



vii 



LIST OF TABLES 

Table Page 

1 - Material sources and designations 143 

2 - Chemical and physical analysis of lime 144 

3 - Analysis of fly ash 145 

4 - Standardization of Harvard miniature compactor 146 

5 - Calibration of extruder 146 

6 - Calibration of miniaturized slump cone 146 

7 - Optimum moisture content for fly ash-lime-sulfate 

mixtures 147 

8 - Density and strength of samples from Ft. Martin fly ash . . . 148 

9 - Density and strength of samples from Black Dog fly ash . . . 149 

10 - Density and strength of samples from Amax fly ash 150 

11 - Density and strength of samples from Albright fly ash .... 151 

12 - Density and strength of samples from Hatfield's Ferry 

fly ash 152 

13 - Comparison of means by least significant difference 153 

14 - Comparison of means for different ashes 154 

15 - Variation in lime/sulfate ratio for Ft. Martin fly ash . . . 157 

16 - Variation in lime/sulfate ratio for Amax fly ash 158 

17 - Density and unconfined compressive strength at various fly 

ash/(lime + sulfate) ratios using Ft. Martin fly ash . . 159 

18 - Density and unconfined compressive strength at various fly 

ash/ (lime + sulfate) ratios using Amax fly ash 160 

19 - Density and strength of compacted specimens with increasing 

sulfate content 161 

20 - Unconfined compressive strength of lime-fly ash and 

lime-sulfate-fly ash mixtures 162 

21 - Density and strength using two calcitic limes 163 

22 - Density and strength using two dolomitic limes 164 

23 - Unconfined compressive strength of mixtures prepared using 

anhydrous calcium sulfate 165 

24 - Unconfined compressive strength for samples cured at 50°F 

(10°C) and 73°F (23°C) 166 

25 - Replacement of lime with portland cement 167 

26 - Influence of admixtures on strength development 168 

viii 



LIST OF TABLES (cont'd) 

Table Page 

27 - Addition of likely impurities and their effect on strength 

development 169 

28 - Systems for compound examination 170 

29 - Compressive strength of compound development specimens . . . 171 

30 - Waste sulfate sources and analysis 172 

31 - Waste sulfate analysis 173 

32 - Strength of specimens prepared using acid mine drainage 

waste 174 

33 - Strength of specimens prepared using industrial wastes . . . 175 

34 - Strength of specimens prepared using gas scrubber waste . . . 176 

35 - Formulations evaluated for engineering properties 177 

36 - Engineering tests performed on selected formulations .... 178 

37 - Summary of strength, permeability and CBR tests 179 

38 - Summary of compacted dry densities and moisture contents . . 180 

39 - Summary of freeze-thaw tests (all samples cured 7 days) . . . 181 

40 - Summary of results of wet-dry tests (all samples cured 

7 days) 182 

41 - Summary of special freeze-thaw and wet-dry tests (28 days 

curing period at 73°F (23°C)) 183 

42 - Leachate analysis 184 

43 - Sulfate soundness test results 185 

44 - Freeze-thaw soundness test results 185 

45 - Concrete mixtures containing cast aggregate 186 

46 - Concrete mixtures containing extruded aggregate 186 

47 - Flow test of fine aggregate mixtures 187 

48 - Concrete evaluation test results 188 

49 - Statistical analysis of concrete strength properties .... 189 

50 - Freeze-thaw test results for concrete 190 



IX 



INTRODUCTION 

In the United States a variety of solid wastes is produced in large 
quantities in industrial and environmental protection operations. Waste 
calcium sulfate is produced in operations which remove sulfur-containing 
materials from power plant emissions and chemical process effluents. Large 
quantities of fly ash are captured from coal-burning power plant emissions. 
Disposal of these materials can give rise to serious ecological problems. 
Thus, it is advantageous to seek uses for these materials, for example, in 
highway construction where they may be substituted for other materials now 
in use. A threefold advantage can be realized: 1) scarce materials can be 
conserved for higher priority uses, 2) environmental damage is minimized and 
3) savings can be effected by using a lower cost material and by the elimina- 
tion of disposal costs. 

A potential use which exhibits significant promise is the mixing of 
sulfate with lime and fly ash to form a pozzolanic type highway construction 
material. This end use is appealing because it can recycle large quantities 
of calcium sulfate and fly ash into a product that can replace presently used 
materials at a competitive price, dependent upon location. 

There have been a limited number of field trials to demonstrate the 
usefulness of using waste sulfate as a building material. In one major demon- 
stration sponsored by the Federal Highway Administration (9) a temporary 
parking area was constructed using approximately 350,000 square yards of a 
lime- fly ash-waste sulfate-water mixture at a compacted depth of five inches. 
Also aggregate was produced and used in test sections for base course compo- 
sitions, bituminous concrete and portland cement concrete. Due to weather, 
subgrade conditions and the non-typical use of the base course (only a pro- 
tective prime coat was used as a wearing course), maximum information on 
waste sulfate utilization was not realized. However, the project did demon- 
strate that lime- fly ash-waste sulfate-water compositions had potential for 
use in highway construction and indicated the need for developing more 
information on the properties and performance of these mixtures. 

The objective of the research was to develop the technology required 
for using sulfate waste in road construction in such applications as 



bases, subbases, and embankments and concrete and bituminous surfacing. The 
research consisted of a laboratory investigation designed to provide back- 
ground information for the practical utilization of sulfate and fly ash wastes 
as binders and aggregate in road construction. This was accomplished by 
first performing a detailed study of lime- fly ash-calcium sulfate-water mix- 
tures to determine the effect calcium sulfate had on lime- fly ash-water mix- 
tures. Included in these studies were variables such as form of calcium 
sulfate, source of fly ash, lime type, curing temperature and admixtures. 
The information gained from these tests were used to choose certain formula- 
tions that were then compounded with waste sulfate rather than pure calcium 
sulfate. Waste sulfates representing a broad range of sources were used in 
this phase. Finally selected formulations were used to evaluate engineering 
properties of these mixtures and to prepare synthetic aggregate. The aggre- 
gate was further tested in Portland cement and asphaltic concrete. 

Waste Sulfate 

Sulfate waste is obtained from industrial process discharges, neutra- 
lized acid mine drainage and power plant scrubbers. In industrial processes 
the main sources are the neutralization of spent sulfuric acid baths, the 
production of phosphoric acid from calcium phosphate and sulfuric acid and 
the production of hydrofluoric acid from calcium fluoride and sulfuric acid. 

Water leaching through abandoned coal mines or coal mine refuse dumps 
emerges laden with sulfuric acid. This waste water, if not treated, serious- 
ly contaminates waterways and destroys aquatic life. The Federal government 
is actively seeking methods to neutralize this acid mine drainage in situ 
(1). A promising technique is to treat the drainage with lime or limestone, 
neutralizing the sulfuric acid and precipitating calcium sulfate. 

Power plants, especially those burning coal, produce stack gases con- 
taining sulfur dioxide pollutant. An increasing number of power plants are 
equipped with "scrubbers" to remove sulfur dioxide from the stack gas (2-5). 
In one type of desulfurization process, lime or limestone is injected into 
the boiler and reacts with sulfur dioxide to form calcium sulfite and calcium 
sulfate. These materials may be collected separately or may be collected 



with the other particulate matter, primarily fly ash, that emerges with the 
gaseous discharge. If collected with the fly ash, a product called "limestone 
(or lime) modified fly ash" is formed. 

When this report was prepared, there were seventeen power plants either 
planned or in operation equipped with these scrubber systems (3) . None of 
this modified fly ash was being used commercially although studies (6, 7) had 
been conducted to find economically feasible uses for it. According to Cock- 
rell et al. (7), the utilization method with greatest promise was found to be 
the Conceptual Emission Control Minerals Complex method which makes use of 
all fractions of the ash. Other promising methods suggested included taking 
advantage of the pozzolanic properties of the ash to form structural and 
"concrete products. A research and development program to find uses for this 
material in the construction fields has been suggested (2). 

Fly Ash 

Some modest success has been found in recycling fly ash with 1.6 to 
2 million tons of the approximately 26.5 million tons collected annually in 
the United States being used commercially (2). Impediments to the further 
use of fly ash are lack of proper quality control by the producer, difficulty 
in handling, previous misuse of the material and lack of utilization tech- 
nology. 

Utilization technology has been well advanced in the area of lime- fly 
ash-aggregate base course construction. Its use by state highway departments 
in actual operations is not extensive, however, because of a lack of famil- 
iarity with this material in the field. Also, strength development is slow. 

An improved quality base course can supposedly be produced by introduc- 
ing calcium sulfate into the lime-pozzolan mixture (8) . Development of such 
a material, followed by an educational program and construction demonstrations 
for potential users, might accelerate the widespread use of this material in 
highway construction. This would allow recycling of large amounts of waste 
materials in highway construction and provide highway builders with an addi- 
tional acceptable material to use as conditions warrant. 



EXPERIMENTAL PROCEDURES 



Materials 



Four limes, four pure sulfate sources and five fly ashes were used in 
this study. The sources of all these materials and their shorthand designa- 
tion that will be used for identification are shown in Table 1 (page 143) . 

The four hydrated limes were obtained from commercial sources and used 
as received. Both calcitic and dolomitic limes were chosen. Their proper- 
ties are presented in Table 2 (page 144) . 

Four different calcium sulfate/sulfite sources and materials were used. 
There were two sources of gypsum; one a precipitated, finely powdered product 
and the other obtained from a commercial mining operation. The other two 
pure materials used to simulate waste sulfate were anhydrous calcium sulfate 
and calcium sulfite hemihydrate. This last material was chosen for study due 
to the possibility of it being formed as the main waste product in gas 
scrubbers . 

Five low carbon fly ashes from various power plants in the East and 
Mid-west were chosen for study. These included four bituminous and one 
sub-bituminous fly ash. The bituminous ashes were donated by the Allegheny 
Power Service Corp. and Monongahela Power Company. They were from the Fort 
Martin Power Station, Hatfield's Ferry Power Station and Albright Power Sta- 
tion. Ash from the Mitchell Power Station is marketed through the Amax Fly 
Ash Corp., New Eagle, Pa. Fly ash from sub- bituminous coal was obtained from 
the Northern States Power Company at its Black Dog Power Station. Analyses 
of the ashes are presented in Table 3 (page 145) . 

All the ashes were low in carbon (less than six percent), and varied in 
chemical composition. The important components, aluminum, silicon, iron and 
calcium, were of differing proportions in each ash. A survey revealed the 
greater importance of physical factors versus chemical variations in lime- 
fly ash reactions. Accordingly, ashes were chosen to investigate these 
differences. Thus, Amax and Hatfield's Ferry fly ash have similar chemical 
composition but vary in physical properties. 



In addition to the above materials, the following reagent grade chemicals 
were included for particular experiments: aluminum hydroxide, aluminum sul- 
fate, calcium carbonate, calcium fluoride, ferric nitrate, sodium carbonate 
and sodium hydroxide, Fisher Scientific Co.; Portland cement, Type I, Martin 
Marietta Co.; Darex® Set Accelerator, a calcium formate formulation, W. R. 
Grace & Co. 

Ferric hydroxide was freshly prepared by; 1) the dropwise addition of 
concentrated ammonium hydroxide to a solution of ferric nitrate and 2) the 
addition of a stoichiometric amount of sodium carbonate to a ferric nitrate 
solution. The pH of the resultant slurry was used to indicate neutralization. 



Engineering Test Methods 

Compaction 

Samples of a compactible consistency were prepared with a modified 
Harvard Miniature Compaction Apparatus as developed by the Virginia Highway 
Research Council (10). The procedure was modified by using a one pound ham- 
mer instead of the spring- loaded tamper. This apparatus was used to simu- 
late the compactive effort of AASHTO T- 180-731, "Moisture Density Relations 
of Soils using a 10- lb. Rammer and an 18- in. Drop." Five layers were used 
with the number of blows per layer adjusted to obtain the same density as 
a regular mold and hammer on test samples. 

A mixture of 80 percent fly ash, 10 percent lime and 10 percent gypsum 
at 18 percent moisture content was used for calibration purposes. This 
mixture was compacted by the standard procedure in a cylindrical mold, 
4 inches high by 4 inches in diameter. Then fresh mixture was compacted in 
the Harvard miniature mold in five layers at a varying number of blows per 
layer. Table 4 (page 146) presents the average wet density for duplicate 
samples at varying blows per layer. From this experiment it was decided to 
use 40 blows per layer when preparing compacted specimens. 

Extrusion 

A three inch diameter, model PX-3 extruder manufactured by Fate-Root- 
Heath Company, Plymouth, Ohio was used for the extrusion experiments. This 
machine operates by feeding the material by an auger arrangement through 



a vacuum chamber with the material finally compacted in another set of augers 
and forced through the die. For studies of mixtures at an extrudable consis- 
tency, a one inch diameter die and augers designed for manufacturing ceramic 
materials were used. 

The extruder was calibrated by measuring the weight of wet fly ash 
forced through the one inch die at various speed settings. The data pre- 
sented in Table 5 (page 146) were the average of at least three determina- 
tions. At maximum setting the machine could operate at slightly greater 
than 45 kg (100 lbs) per hour. For the bulk of the work reported here, 
setting 3 was used since it produced extrudate at a manageable rate. 

Slump Determination 

As with the compactible consistency, a miniature apparatus was used for 
preparing samples after calibration against the standard equipment. The 
specification followed was AASHTO T- 119-70, "Slump of Portland Cement Con- 
crete." The new cone used was 6 inches high with upper and lower diameters 
of 2 and 4 inches, respectively, and having a volume of 0.026 cubic feet. 
The slump of each mixture was measured before samples were molded, ensuring 
the proper moisture content of each sample. 

A calibration curve was constructed by measuring the slump of fly ash 
and water mixtures in both the miniature and standard size cones. The data 
obtained are presented in Table 6 (page 146 ) with the calibration curve 
reproduced in Figure 1 (page 89). A slump of one and three eighths inches 
with the small slump cone corresponded to a mixture at three inch slump con- 
sistency using the standard slump cone. 
Strength Specimen Preparation 

For all mixture consistencies, preparation began identically. The dry 
ingredients; fly ash, lime and sulfate, were weighed and placed in the mixing 
bowl of a Hobart Model N-50 mixer. Dry blending at low speed proceeded for 
one minute. The deionized water was added and mixing continued for another 
two minutes . 

For compactible consistency, enough material for preparing strength 
specimens was placed in jars. Two moisture content samples were taken. 



Sample compaction followed. After each specimen was compacted it was weighed 
and then wrapped in Saran Wrap and sealed with tape. They were then ready 
for storage in the proper temperature cabinet, generally at 73 ± 3°F (23°C) . 

For extrudable consistency, more water was needed than for compactible 
consistency. A mixture was considered to be extrudable if the column pro- 
duced held its shape on standing and was not so dry that it crumbled upon 
leaving the die nor so wet as to bleed upon standing. An extrudable mixture 
coming from the machine is shown in Figure 2 (page 90 ) . Due to difficulties 
caused by the particular design of augers and dies resulting in excessive 
compaction and materials drying in the machine, most of the samples formed 
were at the high end of the moisture boundary. This was equivalent to a 
slump of less than one inch. When preparing strength specimens, a plastic 
cylinder the same diameter as the die was held at the end of the machine. 
This cylinder, one inch in diameter and approximately 2.5 inches long, was 
made by removing the bottom from a 9 dram snap-cap vial. As soon as the 
cylinder was filled and there was no evidence of air bubbles in the cylinder, 
the column was cut. The vial cap was replaced and sealed with melted paraf- 
fin wax. The other end of the mold was covered with Parafilm®. Then the 
whole specimen was further enclosed in a rubber finger cot and totally 
sealed with more paraffin wax before placement in the proper temperature 
environment. Two or three moisture content samples were removed from the 
extruded column during the specimen preparation period. 

For specimens the consistency of three inch slump concrete, the slump 
was measured with the miniaturized cone after mixing with water. At the 
proper consistency, moisture content samples were removed. The strength 
specimens were then formed by packing the material, with rodding, into a 
specially designed mold. The mold was fabricated from a plastic, nine- 
dram snap-cap vial as explained previously. The only difference in use was 
that the snap-cap was in place and sealed with wax before the slump mixture 
was compacted in it. In this way the original top of the vial was now the 
bottom. Sealing of the specimens for curing was done in the same way as for 
extruded samples. 



Density Determination 

For compactible mixtures, the dry density of each specimen could be 
directly calculated from the sample weight and moisture content. For the 
extrudable three-inch slump consistency, due to lack of uniformity of the 
mold length, a sample was cast and the density determined after hardening. 
The method followed was AASHTO T-233-70, "Density of Soil-In-Place by Block, 
Chunk or Core Sampling." 

Strength Measurements 

The unconfined compressive strength and split tensile strength were 
measured on an Instron Model TT-D, Universal Testing Instrument. A constant 
loading rate of 0.2 cm/min (0.08 in/min) was used. 

For the split tensile strength, the cylindrical specimen was placed on 
its side with its horizontal axis between the platens of the Instron Testing 
Instrument. Two strips of balsa wood, between the specimen and each of the 
two platens, acted as a bearing material. Under proper alignment, fracture 
occurred along the loaded diameter as a result of tensile stresses which 
develop across this diameter. The splitting strength was calculated from 
the following equation: 

2P 
Splitting Strength = 



77DL 



where P = load on specimen at splitting, lbs. 
L = length of specimen, inches 
D = diameter of specimen, inches 

All strength data reported were the average of three specimens prepared 
from the same formulation and the same batch. In addition, each specimen 
was weighed before testing to verify that no significant weight loss 
occurred while curing. If a specimen showed excessive weight loss, it was 
discarded and another specimen substituted. I 

Dimensional Changes 

The length and diameter of selected compacted cylinders were measured 
at the time of compaction and then at time of strength measurement. A 

8 



vernier caliper and specially designed sample holder were employed in this 
operation. The sample holder shown in Figure 3 (page 91 ) was a machined 
plate with two separate guide-grooves for proper caliper placement. With 
the sample resting against the zero-stop, these grooves were at a distance 
of one- third and two-thirds the total sample height. For each specimen, the 
diameter at one-third and two-thirds height were measured and then repeated 
after rotating the specimen by ninety degrees on the long axis. Length 
measurements of these cylindrical specimens were also obtained using values 
from two measurements taken at right angles to each other. 

Compound Identification 

Fresh specimens were prepared for use in compound examination. They 
were fabricated, cured and tested for compressive strength as described 
previously. Then the specimens were broken into small chunks and placed in 
a vacuum drying oven at 35 °C for at least 12 hours. After drying, samples 
were removed and sealed in a vial until examined by scanning electron micros- 
copy. The rest of the specimen was pulverized to pass a 60 mesh screen 
using a Wiley Mill. The resultant powder was sealed in plastic bags until 
used. These samples, as well as the starting materials, were examined by 
x-ray diffraction, differential scanning calorimetry and thermogravimetric 
analysis. 

The x-ray diffraction studies were made on a wide range diffractometer 
manufactured by the Picker Company, with a copper x-ray tube (CuK = 
1.54178A). The instrument was run at 45 kv, 11 mA, zero suppression, 0.6° 
slits were used, Ni filters, a scanning speed of 2°/28/niinute, 100 counts 
per second full scale deflection and a time constant of 2. 

Specimens had previously been crushed to pass through 60 mesh sieves 
and vacuum dried at room temperature, in order not to decompose hydrates 
such as ettringite. The portion to be used was ground finer for about 1/2 
minute in an agate mortar and pestle before mounting on a glass slide using 
a smear of the powder in acetone, which evaporated to leave a thin solid 
film. 



A few of the specimens were studied using a GE XRD-3 diffractometer 

with CuK radiation run at 40 kv and 17 mA. A 0.1° slit was normally used. 

a 

Scanning speed was 2°/2Q/minute at 100 cps. Some samples were run in dupli- 
cate on the two instruments to provide calibration. 

For examination by scanning electron microscopy (SEM) , specimens were 
mounted on a carbon stub with a silver containing adhesive. They were then 
coated with carbon and approximately 200 A of go Id -palladium. The instrument 
used was the JEOLCO Model JSM-2, operated at accelerating voltages of 15 kv 
and 25 kv. Elemental analyses were performed with an EDAX retractable, 
energy dispersive, x-ray detector. 

Thermal analysis was performed using a Perkin-Elmer Model TGS-1 Thermal 
Analysis System and a Model DSC- IB Differential Scanning Calorimeter. The 
temperature range from 25 to 500°C was scanned at a rate of 10°C/minute. 



10 



EXPERIMENTAL RESULTS 
Development of an Optimized Lime-Fly Ash-Calcium Sulfate System 

Moisture-Density Relationship 

To determine the optimum moisture content for compacted specimens the 
moisture-density relationship was investigated. The procedure specified in 
AASHTO T- 180-731, was followed using the miniaturized equipment. A mixture 
of 80 percent fly ash, 12 percent gypsum and 8 percent lime was used for each 
of the fly ashes. Also determined were moisture-density relationships for 
mixtures of 92 percent Fort Martin fly ash, 2.7 percent lime and 5.3 percent 
gypsum and 92 percent Amax fly ash, 3.2 percent lime and 4.8 percent gypsum. 
The optimum moisture contents varied from 19.5 to 24.5 percent (Table 7, 
page 147) for the five fly ashes but was constant for different proportions 
using the same dry materials. These values were obtained from the maxima of 
the plots presented in Figures 4-7 (pages 92 to 95 ) , with the data in 
Appendix A. 

Full Factorial Experimental Design 

The use of a factorial experiment permits one to evaluate the combined 
effects of multiple experimental variables when used simultaneously. It 
permits the evaluation of main effects and interaction effects, that is, an 
effect attributable to the combination of variables above and beyond that 
which can be predicted from the variables considered singly. One formulation 
was chosen which consisted of 12 percent lime, 8 percent sulfate and 80 per- 
cent fly ash. The lime level was high enough to determine the relative 
pozzolanic reactivity of the fly ashes. Also some of the data from the 
series of experiments could be used in the next series of experiments for 
optimizing the lime /sulfate ratio. 

The main effects under investigation using the full factorial design 
were lime type, form of calcium sulfate or calcium sulfite, fly ash source 
and water level. Compressive strength development after 7, 28 and 91 days 
of curing was measured for samples prepared from all possible combinations 



11 



of two limes, three sulfates and the five fly ashes. All three consisten- 
cies were used except for extrudable with Black Dog fly ash. The two limes 
chosen were hydrated calcitic (A^ and monohydrated dolomitic (A 2 ) vari- 
eties. Three sulfates were included in the evaluation. The first, B, , was 
a finely precipitated material. The second, B~, was commercial grade gypsum, 
The third, B , was calcium sulfite and it was included in the full factorial 
experiment since it can be the major constituent of gas scrubber sludge, a 
very important waste sulfate source. 

Tables 8-12 (pages 148 - 152) contain the data for this first set of 
experiments. Moisture content, dry density and compressive strength at 7, 
28 and 91 days were measured. Histograms of the strength data are presented 
in Figures 8-12 (pages 96 to 100 ). 

The moisture content and dry density data appear to exhibit identical 

behavior. Both these values were similar for extrudable and slump data 

while being greatly different from the compactible consistency. The 7 day 

strength data indicated that extrudable and slump consistency were nearly 

identical and both greatly different from the compactible consistency. The 

range in 7 day strength values for extrudable and slump was 30 to 150 psi 

2 
(207-2,458 kN/m ), while for compactible it was 160 to 695 psi (1,102-4,789 

2 

kN/m ) . It was observed when unwrapping the slump and extruded specimens 

that a majority of them were still visibly moist. In a few cases at the 
three inch slump consistency, the excess water had pooled on the top of the 

specimen. By 91 days, the strengths obtained ranged from 1300 to over 5000 

2 

psi (8,957-34,450 kN/m ). However, it was the compactible samples that con- 
sistently gave the highest average strength. 

The statistical tool used to evaluate the results of the compressive 
strength data was the analysis of variance, which is ideally suited for 
factorial design. The purpose of the analysis was to supply criteria for 
determining whether a given variable or factor was influencing the results. 
The significance of factors or variables was tested by applying the F ratios 
first between the interaction of factors, then main factors and the pooled 
term or the mean square error term. The mean square error term represents 



12 



the experimental error. When the F ratio shows significance for the factor 
the levels or component parts of it can then be analyzed several ways. 

The total 7 day strength data were analyzed by a four way analysis of 
variance, and the 7 and 28 day compactible data was analyzed by a three way 
analysis of variance. Since it was noted that the range of the replicates 
divided by their mean was approximately a constant, a logarithmic transfor- 
mation was indicated (11). This transformation was performed on the data 
before analysis. Appendix B contains the computed mean square data. For 
the total 7 day strength data, it was found that at the 95 percent confidence 
level, all main effects and all interactions were significant. 

The data were then separated so that only the compactible data were 
analyzed. Again, at 7 days all main effects were significant but now the 
fly ash-sulfate interaction was not significant. For the 28 day data, the 
analysis inidcated that now, the main sulfate effect was not significant. 
Therefore, by 28 days it did not matter if calcium sulfate or calcium sulfite 
was used. Next we attempted to determine if any difference existed between 
the different materials in each group. An analysis involving the use of the 
Least Significant Difference of the individual means was performed using the 
following equation: 

LSD = fS D 

where t is the value of students t and S is defined as 

S^ = 



■.- v? 



2 
where S is the pooled mean square error and N is the number of values going 

into each mean. 

This type of analysis has been performed for strength data from 7 days 
and 28 days at a compactible consistency. Table 13 (page 153) presents the 
findings using the data found in Appendix B. The conclusions from this 
analysis are: 

13 



1. Both limes were different, the dolomitic monohydrate being 
better at 7 days and the calcitic better at 28 days. 

2. At 7 days both the ground gypsum and finely precipitated 
gypsum were comparable and better than calcium sulfite. 

At 28 days there was no difference between calcium sulfate 
and calcium sulfite. 

3. The fly ashes that gave the highest early strength were 
Amax (C 3 ) and Ft. Martin (C.,) , with Black Dog (O , 
Hatfield's Ferry (C,-) and Albright (C.) following in 
that order. By 28 days Ft. Martin (C^) still gave the 
highest strengths with Amax (C_) second, Black Dog (C«) 
and Hatfield's Ferry (C<-) together being third and 
Albright (C.) still last. 

To evaluate further the differences between components of the main vari- 
ables, the least significant difference test was run on 7 and 28 days 
strength data for compactible mixtures that was analyzed separately for 
each fly ash. The object was to determine if the rankings for the materials 
within each main group was the same for each fly ash. This would uncover 
the situation of finding two materials significantly different because the 
reaction with one of the five fly ashes was so different. Table 14 (page 
154) reports the results of this evaluation. 

The dolomitic lime was determined to be more reactive than calcitic 
lime at 7 days as shown in Table 14 (page 154) . When the results were 
evaluated for each individual ash, it was noted that this result was true 
for three ashes. The only two exceptions were the first ranked ash, Amax, 
which was as reactive as with calcitic lime and Black Dog, the sub- bituminous 
fly ash for which the calcitic lime was more reactive. The two gypsum 
sources were indistinguishable for each fly ash and better than the calcium 
sulfite. At 28 days, the calcitic lime was reported to be better than the 
dolomitic lime when the fly ashes were considered in a group. When evalu- 
ated individually, the limes were not significantly different in three cases 
and the calcitic lime better in two cases; a) with Amax, the second ranked 



14 



ash and b) with Black Dog, the sub-bituminous ash. The sulfates, which were 
all determined to be identical in the full array, were found to be identical 
with three of the ashes. However, with Amax fly ash the commercial gypsum 
was found to be different while with the poorest ash, Albright, calcium 
sulfite still gave the lowest strength. Therefore the general findings of 
differences and similarities among the materials in each main effect were 
not caused by just one, different fly ash. 

Optimizing the Lime/Sulfate Ratio 

With some knowledge of the starting materials, attention was turned to 
optimizing the mixture composition to obtain maximum compressive strength. 
The first step in this process was to keep the fly ash content constant (at 
80 weight percent) and to vary the amount of lime and sulfate. By this 
method the range from a large amount of lime and very little sulfate, to a 
very low lime level and a large amount of sulfate was covered. This process 
would aid in determining the relative amounts of lime and sulfate that form 
the most reactive composition. 

Ft. Martin and Amax, two of the better fly ashes, were chosen for 
studies to optimize the lime/sulfate ratio. Gypsum was used as the sulfate 
source, and both types of lime were used. Specifically, Ft. Martin fly ash 
was examined with calcitic lime and ground gypsum (A.. B„ C-) while Amax fly 
ash was used with dolomitic lime and ground gypsum; (A~ B_ C_) . All mois- 
ture contents, viz., optimum, extrudable and three inch slump, were used. 
With the compactible mixtures, the lime to sulfate ratio was diminished from 
the full factorial design experiment since compressive strengths were quite 
high and maximization at a lower lime level was desired. For extrudable three 
inch slump consistency, the lime/sulfate ratio was decreased and increased; 
the rationale here being to determine the lower limit as well as to examine 
systems to be used in aggregate production where greater strengths are needed. 

Samples for strength evaluation were fabricated as previously described 
and cured at 73°F (23°C) . They were tested for unconfined compressive 
strength at 7 and 28 days. The results for the two ashes are presented in 
Tables 15 and 16 (pages 157 - 158 ) . 



15 



For the compactible mixtures, plots of lime/sulfate ratio versus uncon- 
fined compressive strength are in Figures 13 and 14. For seven day strengths, 
the Ft. Martin ash showed no variation from a ratio of 0.1 to 1.0, with a 
slight decrease thereafter. However, for 28 day strengths, there was a large 
increase with increasing ratio, reaching a maximum value at a ratio of about 
1. For the Amax ash the situation was quite similar. Seven day strength 
data were fairly uniform, with a maximum at about 0.67, though not well de- 
fined. However, 28 day data showed large variations of strength with lime/ 
sulfate ratio. And again the highest strength was obtained at a ratio of 1. 

For the extrudable mixtures, plots of lime/sulfate versus compressive 
strength are given in Figures 15 and 16. The 7 day data were all low and 
did not follow a regular pattern. As indicated before, these samples were 
soft and the strength was most likely more a consequence of the consistency 
rather than the materials. At 28 days, the curves for both ashes were quite 
similar, being at a maximum somewhere between a ratio of 1.5 and 4.0 The 
Amax ash was used in combination with calcium sulfite which, from the analyses 
of the full factorial experiment, should not be significantly different from 
the other sulfate sources at 28 days. 

For the three inch slump consistency, the general observations made for 
the extrudable consistency still hold. The 7 day compressive strengths were 
low and did not follow a regular pattern. The 28 day strengths also exhibited 
the same general behavior (Figures 17 and 18, pages 105 - 106), having a 
maximum between the ratios of 1.5 to 4.0. With regard to the optimum lime/ 
sulfate ratio the formulations at a compactible consistency reached a maximum 
strength at a lower ratio than both the extrudable and three inch slump 
formulations. 

Optimizing the Fly Ash/ (Lime + Sulfate) Ratio 

The next series of experiments entailed varying the fly ash/ (lime + 
sulfate) ratio at a constant lime/sulfate ratio. 

The previous set of experiments was necessary to determine the correct 
proportions of the two reactants, lime and gypsum, that were most critical 
for the chemical reactions. Now, with the optimum ratio determined, the 

16 



amount of fly ash could be varied to determine the effect of binder level 
(lime and sulfate) on compressive strength. This would provide information 
not only on the optimum composition but also on the range of compositions 
that would be applicable to different areas of highway construction. 

For mixtures at a compactible consistency prepared with Ft. Martin fly 
ash, the ratio of lime to sulfate was kept at 1/2. This choice was made 
after the 7 day strength data was available. Examination of those values 
showed very little variation in strength with change in lime and sulfate 
proportions. The relative amounts of lime to sulfate was held at 1 to 2 in 
order to keep the percentage of lime at a reasonable level when the fly ash/ 
lime + sulfate) ratio was increased. The data for Ft. Martin fly ash are 
presented in Table 17 (page 159) and plotted in Figure 19 (page 107) . The 
ratio of fly ash/ (lime + sulfate) was varied from 4 to 11.5. The 7 day data 
showed a slight increase as the ratio was increased. The 28 day data showed 
the strength decreasing with fly ash content. This type of behavior was not 
unexpected since the lime and gypsum were the main cementing agents and most 
of the fly ash could be considered as unreacted filler. 

Amax fly ash was also evaluated for the effect of changes in the fly ash/ 
(lime + sulfate) ratio. A constant lime/sulfate ratio of 2/3 was chosen. 
Table 18 (page 160) reports the results obtained from varying the fly ash/ 
(lime + sulfate) ratio at this fixed lime/sulfate proportion. The 7 day 

strengths increased with increasing ratio up to 92 percent ash, and then 

2 

decreased for the next data point. The value of 570 p.s.i. (3927 kN/m ) at 

86 percent fly ash was most likely a consequence of its higher density. The 
strength at 7 days, using Amax fly ash, was seen to be near a maximum at a 
composition consisting of 3.2 percent lime, 4.8 percent gypsum and 92 percent 
fly ash. Thus, for a system of pure materials, early strength was maximized 
at a reasonable level of lime, utilizing a large amount of fly ash and a 
moderate amount of calcium sulfate. 

The 28 day strengths exhibited the same behavior with Amax fly ash as 
already mentioned for Ft. Martin fly ash, namely, the less lime and gypsum 
the lower the strength. This is shown in Figure 20 (page 108). 



17 



Extrudable mixtures were studied with only the Ft. Martin fly ash, 
dolomitic lime and ground gypsum. A lime/sulfate ratio of 3/2 was chosen 
for this water level. This ratio was near the maximum as found in the pre- 
vious series of experiments. The fly ash/ (lime + sulfate) ratio was varied 
from 1.5 to 9 and the results of the strength tests are reported in Table 17 
and plotted in Figure 21 (page 109). The 7 day strengths, as with all others 
at extrudable and three inch slump consistency, were low and not dependent 
upon the amount or type of fly ash. For the 28 day strengths, the curve 
reached a maximum at a ratio of about 3.5. This would correspond to a com- 
position of 13.2 percent lime, 8.8 percent gypsum and 78 percent fly ash. 
This result differed with the compactible consistency in that the strength 
did not just decrease with increased fly ash content. 

Three inch slump consistency was examined with Amax fly ash, dolomitic 
lime and ground gypsum while Ft. Martin fly ash was studied in combination 
with calcitic lime and ground gypsum. The data are reported in Tables 17 
and 18 with the appropriate plots in Figure 22 (page 110) . A constant lime/ 
sulfate ratio of 3/2 was chosen for Amax fly ash while a ratio of 2/3 was 
used for Ft. Martin Fly ash. The strength results at 7 days were not very 
meaningful, again, due to the consistency of the sample, that is the samples 
were still wet and it was the state of the sample, rather than any cementi- 
tious reactions, that was being measured. The 28 day strength did go through 
a maximum in the range examined at a fly ash/ (lime + sulfate) ratio near 5 
for the Amax formulation. This would correspond to a composition of 10.2 
percent lime, 6.8 percent sulfate and 83 percent fly ash. For the Ft. Martin 
formulation, the maximum was at a ratio near 4, or 8 percent lime, 12 percent 
gypsum and 80 percent fly ash. Therefore, the three inch slump consistency 
resembled the extrudable consistency and not the compactible formulation in 
that a maximum strength was encountered in the range examined. 

Maximizing the Sulfate Content 

The goal of the next set of experiments was to determine the maximum 
amount of gypsum that could be added to lime- fly ash-sulfate-water mixtures 
at a compactible consistency and still produce strengths comparable to mix- 
tures without sulfate present. Results of the previous experiments showed 
that respectable strengths were achieved with lime levels from three to five 

18 



weight percent of the dry mixture at a compact ible consistency. Two formu- 
lations were studied. In one, Amax fly ash, dolomitic lime and ground gypsum 
were used, with the fly ash/lime ratio held constant at 28.5. This corre- 
sponded to a lime content of roughly three percent. The other formulation 
used Ft. Martin fly ash with calcitic lime and the finely precipitated gypsum. 
It had a constant lime level of 4.7 percent. The data for these two studies 
are reported in Table 19 ( page 161 ) and plotted in Figures 23 and 24 (pages 
111 to 112). 

For the Amax fly ash, the addition of gypsum from five to nine percent 
increased the strength over the composition without gypsum at seven days. 
For the last two entries, the strengths were comparable to no gypsum addi- 
tion. However, the lime content was about 15 percent lower. By 28 days, all 
formulations with gypsum in them up to 17 percent had greater strengths than 
the lime- fly ash-water system. For additions of gypsum in the range of 5 to 
10 percent, the strength was at a maximum. It was not until the 13 percent 
gypsum addition that the strength decreased. 

For the Ft. Martin fly ash, the additions of gypsum had a positive effect 
on strength development at both 7 and 28 days. Maximum strength occurred at 
a five percent addition level, roughly a lime/sulfate ratio of 1. The Ft. 
Martin fly ash formulation exhibited a greater sulfate effect than the Amax 
fly ash formulation. However, the lime level was also higher in the former 
case. Both sets of runs did show that maximum strength occurred with rela- 
tively small percentages of gypsum addition. Also, at least 15 to 20 percent 
gypsum could be used before the compressive strength decreased to the average 
value of mixtures where no gypsum was present. 

In a different approach, the effect of gypsum on lime-fly ash-water 
mixtures was measured by comparing similar formulations both with and 
without gypsum. Table 20 (page 162) contains the data for this study. 
For the compactible consistency, strength after 7 and 28 days was notice- 
ably higher when gypsum was added to the lime- fly ash-water mixtures for 
both a good ash, CL, and a poor ash, C,.. The 91 day strength values for 
the lime-fly ash systems are included in the Table and they were still 
less than the 28 day strengths when gypsum was added. For the slump 
consistency, the 7 day strengths were comparable (a property of this 

19 



water content) while the above discussion was valid for the 28 and 91 day 
data. 

Lime Type 

In the full factorial experiment, lime type was investigated as a 
variable. The difference between hydrated calcitic lime and monohydrated 
dolomitic lime was examined. In this study, different sources of the same 
type of lime were examined. 

The data in Table 21 (page 163) represents comparative values for 
identical formulations using two different sources of hydrated calcitic 
lime. For the compact ible formulations, lime A_ gave higher 28 day strengths 
than A, . The 7 day strengths at this consistency were comparable, as were 
the dry densities. For slump consistency, lime A., gave better strength 
results at both 7 and 28 days. 

Two dolomitic limes were also compared using identical formulations 
and the results are in Table 22 (page 164). These results show that for 
all cases with compacted specimens lime A~ gave somewhat higher strengths. 
The results from these two studies indicated that other properties besides 
chemical composition, for example, physical properties, were important in 
determining strength development. 

Use of Anhydrous Calcium Sulfate 

There are processes that form calcium sulfate as a waste product at 
high temperatures. At these high temperatures, the gypsum loses its water 
of crystallization and an anhydrous material results. To simulate this 
situation with pure materials, a reagent-grade source of anhydrous calcium 
sulfate was used to totally replace gypsum in lime-fly ash-sulfate-water 
mixtures. Table 23 (page 165) presents compositional and strength data for 
mixtures prepared with gypsum and anhydrous calcium sulfate. The new form 
of calcium sulfate has the designation, B, . The data showed that replacing 
the gypsum in the mixtures gave strengths at 7 days that were, in many 
cases, higher for anhydrous calcium sulfate. This was true even for slump 
consistency. At 28 days, the strengths of compactible specimens were com- 
parable no matter which calcium sulfate was used. However, the 3-inch 

20 



slump consistency specimens had an average lower strength after 28 days of 
curing. 

An equal weight percentage corresponds to a mole ratio of 1.3/1 for 
anhydrous calcium sulfate to gypsum. Examination of Figure 24 (page 112) 
where the effect of sulfate level on strength was plotted suggests that, 
for most of the conditions in Table 23, with the increased calcium sulfate 
content added by using the anhydrous material, the compressive strength 
should be the same, or perhaps a little less than the corresponding gypsum 
formulation. The higher strengths we obtained after 7 days would then 
indicate that the anhydrous form of calcium sulfate was more reactive. 
The lack of difference by 28 days would suggest that by this time, most 
of the unreacted anhydrous salt has been hydrated to form gypsum. 

Low Temperature Curing 

In order to simulate the low temperature curing conditions which may 
be experienced in the field, strength specimens were prepared and cured at 
50°F (10°C). The data from this study are presented in Table 24 (page 166). 
Also included in this Table are strength values of comparable specimens 
that were made from the same materials and cured at 73°F (23°C). Examina- 
tion of the data showed a very definite temperature effect. All of the 
samples of 3- inch slump consistency developed no strength after 7 days. 
Even after 28 days, they did not develop as much strength as similar samples 
cured for only 7 days at 73°F (23°C). Compacted samples exhibited a 
similar pattern. Very low strengths were found after 7 days of curing at 
the lower temperature. At 28 days, the samples had not yet developed as 
high a strength as 7 days curing at 73°F (23°C). The same temperature 
behavior was encountered for 91 days of curing. This longer period of 
curing at 50°F (10°C) produced specimen strengths that were slightly less 
than 28 days of curing at 73°F (23°C). 

Portland Cement Addition 

A series of experiments were run to determine the effect of partial 
or total replacement of lime by Portland cement. These were performed to 
see if further strength development could be achieved by this technique. 

21 



Both poor and acceptable formulations were examined, as were compactible 
and slump consistencies. Table 25 (page 167) contains the data collected. 
Formulations without Portland cement addition were incorporated for compara- 
tive purposes. No dramatic strength differences were noted. The Albright 
fly ash system was beneficiated by this procedure based on 7-day strength. 
At 28 days, the effect was not noticeable. Black Dog fly ash was studied 
in mixtures of 3- inch slump consistency. Here the Portland cement was 
found to be detrimental based on 28-day strengths. Amax fly ash, previously 
found to be one of the most reactive, was also examined. The original 
materials ratio (lime only) used was one of the more acceptable and realis- 
tic formulations. The 28-day strengths did show some improvement when 
lime was replaced. However, it was noted that some specimens were deformed. 
The tops of the specimens had shrunk, giving the appearance of a tapered 
sample. The results from these three systems at 73°F (23°C) showed that 
replacement of lime by Portland cement did not provide great improvements 
and these mixtures should be used with lime as the cementing agent. Perhaps 
the presence of gypsum, which is a known retarder for Portland cement sys- 
tems, prevented the cement from enhancing the strength of these mixtures. 
Also, when it was attempted to use regulated set cement instead of Portland 
cement, it was noted from the tested strength specimens that the cement was 
present in small flakes. This would indicate that at these low addition 
levels, proper dispersion throughout the mixture was not possible with the 
standard mixing technique. 

The last two sets of experiments presented in Table 25 were performed 
with samples cured at 50°F (10°C) instead of 73°F (23°C). The objective 
was to determine if additions of Portland cement would be helpful for ex- 
tending the construction season for lime-fly ash-sulfate-water mixtures. 

For the first set of these studies (at a compactible consistency) the 
data for curing at 73°F (23°C) is reported. It was noted that even with 
total replacement of the lime by Portland cement, the strength obtained at 
the higher curing temperature never developed in the samples cured at 
50°F (10°C). However, the data did indicate that Portland cement was 



22 



beneficial, especially after 28 days of curing. There was almost a direct 
correlation between 28 day stength and Portland cement level. 

For the samples at slump consistency, low strength values were obtained. 
After 7 days of curing, two sets of samples had specimens which were not 
firm enough to obtain any data. The 28 day strength values were also quite 
low and were not much greater than other slump samples cured at 50°F (10°C) 
which had no Portland cement in them. 

Admixtures and Impurities 

Various admixtures were examined for their ability to change the proper- 
ties of lime- fly ash- gypsum-water mixtures. The most important properties to 
achieve were felt to be higher strength, higher early strength and improved 
workability (of the slump mixtures). We were not able to achieve any of these 
goals, as can be seen from the data in Table 26 (page 168). The first two 
formulations in this Table represent mediocre formulations utilizing the poor- 
est fly ashes, while the third was one of the better designs. 

Chemical bases were examined as admixtures since they are reported to 
accelerate the pozzolanic reaction. Sodium carbonate at addition levels 
of 0.5 percent and 1.0 percent was not effective. Even the strong base, 
sodium hydroxide, was found to have no effect at the one percent addition 
level. A source of calcium ions, as exemplified by the set accelerator 
(calcium formate) also did not cause any strength increase. Aluminum 
sulfate which was added to increase the amount of aluminum ions available, 
also showed no effect. Neither a base chemical, set accelerator or water 
reducer had any effect on mixtures at three inch slump consistency. It 
appears that the effect of gypsum on lime-fly ash reactions was so great 
that it was the best "admixture" for these systems. 

To simulate waste sulfates and to determine the effect of the chemical 
constituents that would be expected to be present in these wastes, their 
effect on strength development using formulations prepared with pure gypsum 
was examined. The impurities examined were: 1) calcium carbonate- -to be 
found in wastes where limestone was used for neutralization or S0„ removal; 
2) ferric hydroxide- -expected in neutralized acid mine drainage and 



23 



neutralized steel pickling liquor; 3) aluminum hydroxide- -also a constituent 
of neutralized acid mine drainage; 4) calcium fluoride-- from hydrofluoric 
acid production; 5) calcium phosphate-- from phosphoric acid production; and 
6) ferrous hydroxide — present under certain conditions in neutralized acid 
mine drainage. Strength and density data for these systems are given in 
Table 27 (page 169) . 

At a compactible consistency, calcium carbonate and aluminum hydroxide 
(in a powdered form) were found to have no effect on strength development 
when they replaced part of the sulfate content. A mixture of aluminum 
hydroxide and ferric hydroxide, as well as aluminum hydroxide, ferric 

hydroxide and calcium carbonate were found to have a drastic effect on 

2 
strength development, with only about 200 psi (1378 kN/m ) developing after 

91 days. In these experiments the ferric hydroxide was prepared by neutra- 
lizing a ferric nitrate solution with a stoichiometric amount of ammonium 
hydroxide. Since it was felt that the method of preparation might be 
affecting the results, the experiment was repeated using ferric hydroxide 
prepared by neutralizing ferric nitrate with sodium carbonate instead of 

ammonium hydroxide. When this was done, higher strengths were obtained 

2 
on the order of 550 psi (3,790 kN/m ) after 28 days. Specimens containing 

only ferric hydroxide prepared by sodium carbonate neutralization had an 

2 

average 28 day strength of 475 psi (3,272 kN/m ). Therefore something 

present in the ammonium hydroxide neutralized material was affecting strenth 
development. However, even under the better conditions of ferric hydroxide 
preparation, the specimens developed only about 25 percent of the strength 
than mixtures without it. Ferric hydroxide is a gelatinous material, and 
it was felt that the physical form of the precipitate had great bearing 
on the strength development rather than any chemical interaction. 

Calcium fluoride was examined and found to have only a small deleterious 
affect on 28 day strength. Calcium phosphate was found not to be detrimental 
to the strength properties. In fact, when about half the gypsum was replaced 
by calcium phosphate, the 7 day strength increased significantly (as compared 
to the first entry in Table 27) and the 28 day strength was slightly greater. 
Ferrous hydroxide, prepared by neutralizing ferrous sulfate with sodium 

24 



hydroxide under a blanket of nitrogen, produced low strengths in samples that 
incorporated it. Besides low strength, the 28 day specimens were badly de- 
formed, with cracking and noticeable volume expansion present. Ferrous hydrox- 
ide, as with ferric hydroxide, is a gelatinous precipitate. This could account 
for the lack of chemical reaction and volume stability that had been noticed. 
Quite possibly, the gelatinous material coats the fly ash, lime and gypsum 
particles and impedes the chemical reaction. 



Characterization of Reaction Products in Lime-Fly Ash-Calcium Sulfate Systems 

In order to gain a better understanding of the lime- fly ash-sulfate 
system, certain formulations were chosen for physical, morphological and 
mineralogical evaluation. The objective was to characterize the systems 
morphologically and mineralogically, both initially and after prescribed 
curing regimes, using such techniques as microscopic examination with 
the scanning electron microscope, x-ray diffraction and thermal analysis. 

The compositions that were used and the length of time of curing are 
shown in Table 28 (page 170). To simplify the study, calcitic lime was 
used in all cases. The standard mixture, viz., 4.7 percent calcitic lime, 
9.3 percent precipitated gypsum and 86 percent Ft. Martin fly ash, which 
was chosen for in-depth studies of many of its properties, was also used 
in this characterization program. Another formulation, using the same 
materials but in different ratios was examined. It had less lime and 
more gypsum than the standard mixture. The third formulation was examined 
to learn about the differences when calcium sulfite was used. The formu- 
lation was the same as the standard mixture. The fly ash type was varied 
as indicated by the fourth entry in the Table, with the dry ingredients 
in the same ratio as the standard mixture. Finally, the consistency was 
changed as indicated by the last two entries. Since the slump and 



25 



extrudable consistency were found to differ from the compacted consistency 
based on strength development, a different formulation was used. However, 
the sources of material chosen were the same as before. 

In order to determine the morphological and mineralogical changes that 
were occurring within each mixture as it aged, x-ray diffraction patterns, 
scanning electron micrographs and thermal data were obtained for the start- 
ing materials, uncured specimens, and specimens cured as indicated in Table 29 

Figure 25 (page 113) shows a micrograph of Ft. Martin fly ash. It 
consisted mainly of spherical particles of varying sizes. Also seen was 
an amorphous material usually as a coating on a sphere or on several spheres. 
The x-ray diffraction pattern for this ash indicated small quantities of 
mullite, quartz and an iron oxide phase to be present. 

The gypsum used is shown in Figure 26 (page 114) . Well developed 
crystals were found throughout this sample. X-ray diffraction showed that 
calcium sulfate hemihydrate was present in very small amount as the only 
impurity. 

The last major ingredient, lime, is shown in Figure 27 (page 115). 
It has a much smaller particle size than the fly ash or gypsum and the 
crystal structural features were not well defined, even at higher magni- 
fications. A small quantity of calcite, as exhibited by an x-ray diffrac- 
tion peak at 29.4° 2Q was evidence that some carbonation had taken place. 

The formulation examined the most extensively was the standard mixture. 
At zero days, the x-ray diffraction pattern exhibited peaks for Ca(0H) 9 , 
CaSO, *2H_0, mullite, magnetite, hematite and quartz, the last four minerals 
arising from the fly ash. Figure 28 (page 116) presents the diffraction 
pattern from 10°-30° 2 Q for the uncured mixture. The major peaks were 
lime (18.1°), gypsum (11.7°, 29.2°, 20.8°, 23.4°), mullite (26.4°, 26.1°, 
16.5°) and quartz (26.7°). Examination of the SEM photograph, Figure 29 
(page 117) revealed quite clearly the fly ash spheres and the gypsum 
crystals. The lime was not immediately evident due to its smaller crystal 
size. Thermal analysis by differential scanning calorimetry (DSC) showed 
one peak at 135 °C which could be ascribed to gypsum. After 7 days, the 



26 



diffraction pattern in Figure 28 was obtained. The most noticeable features 
of this spectrum were the absence of the lime peak and the decrease in the 
intensity of the gypsum peaks in relation to the quartz and mullite. Even 
the most intense lime peak at 34.1° 2Q was only five divisions above the 
base line. 

The SEM photograph of this mixture, Figure 30 (page 118), did not 
indicate any gross changes in properties. Gypsum particles were seen to 
undergo deterioration with loss of the well defined crystal structure seen 
at zero days. No new phases were immediately obvious at this magnification 
at this time of curing. However, the DSC trace did show a small endothermic 
peak centered around 95 °C. 

There was not much change in the diffraction pattern at 28 days as 
compared to 7 days as is seen in Figure 28. Lime peaks were absent by 28 
days, while the gypsum peaks were ( still present. The relative gypsum 
content as compared to the quartz and mullite peaks did not seem signifi- 
cantly different between 7 and 28 days of curing. No new phases were identi- 
fiable by this technique. However, the SEM pictures did show gross changes, 
as seen in Figure 31 (page 119). Here, a new phase had developed between 
the particles. The extent of development can be judged by examining the 
area to the right of the fly ash sphere in the center. All the material 
in that area is new. The hole was where the fly ash sphere had resided. 
Since this was an internal surface, the fly ash sphere itself was most 
likely retained on the other half of the fracture surface or loosened and 
removed during fracture and subsequent handling. Besides all of the new 
solid material present, it was interesting to note that the fly ash parti- 
cles that were visible were still spherical, with no indication of surface 
attack, though some aluminum or silicon must have dissolved from the fly ash, 

The appearance of the new crystal phase was further elucidated by 
examining the specimens at higher magnification. Figures 32 to 35 (pages 
120 to 123) present photographs at 6,000 magnification for mixtures cured 
at 0, 7, 14 and 28 days, respectively. The first of these pictures shows 
an uncured specimen. Immediately obvious were the fly ash spheres and a 



27 



gypsum lath. In Figure 33, at 7 days, the appearance of this new phase 
on the fly ash spheres was obvious. The subsequent Figures showed the in- 
creased growth of these needlelike crystals. Returning to Figure 33, it 
can be seen that the crystals growing from the fly ash sphere surface into 
the pore structure intertwine when two fly ash spheres were in close prox- 
imity. This would afford mechanical stability to such systems and would 
account for the strength increases at early time intervals. 

The DSC trace at 14 and 28 days showed two endothermic peaks, 
one at 100 °C and the other at 135 °C. The higher one was from gypsum while 
the lower one was presumed to come from this new phase. The height of the 
lower temperature peak increased with increased curing time, indicating that 
this new phase was continuing to increase in abundance. 

By 91 days, the x-ray diffraction pattern still did not show any 
striking differences. Figure 28 indicated that the lime was no longer 
present. Gypsum was still quite recognizable. No new compounds were 
immediately obvious. However, the SEM did indicate that changes had con- 
tinued. One of the most striking features of the micrograph shown in 
Figure 36 (page 124) was the lack of visibility of fly ash spheres. The 
reaction product had encased the majority of them, and constituted the 
major feature of the micrograph. The extent of reaction can be judged by 
the rim of reaction product visible in the lower center portion of the 
Figure. The crystal mass from this sheath was seen to interact or inter- 
mingle with the crystals from the fly ash sphere that were in the lower 
right corner. 

With the gross changes found between an uncured mixture and the same 
mixture cured for 91 days at 73°F (23°C), the identity of the new phase was 
still not apparent. Due to the effect calcium sulfate produced on the com- 
pressive strength measurements at the early time periods, and the appearance 
of this new crystal phase as early as 7 days, it was felt that this new 
phase most likely contained sulfate in some form. Examination of the liter- 
ature indicated three major forms in which the sulfate could be present. 
Tetracalcium aluminate monosulfate- 12-hydrate was possible. It has its 
strongest x-ray diffraction peak at a d-spacing of 8.90 A which corresponds 

28 



to 9.8° 2Q. Tetracalcium aluminate monosulfate-14-hydrate was stable under 
the conditions used for curing. Its x-ray basal spacing is 9.5 A or 9.3° 
2$. The third major compound possible was ettringite, or 6-calcium alumi- 
nate trisulfate-32-hydrate. 9.1° 2$ which corresponds to a d-spacing of 
9.73 A is its major peak. 

The probability of the monosulfate forms being present can be tenta- 
tively ruled out. The amount of gypsum in the original mixtures was more 
than necessary to form the high sulfate form. Also, unreacted gypsum was 
still present in the mixtures, as exmplified by the XRD patterns and DSC 
traces. Therefore, the possibility of ettringite being present was pursued. 

To ascertain the amount of ettringite needed to give a characteristic 
x-ray diffraction pattern in lime- fly ash-sulfate mixtures, a sample of 
pure ettringite was obtained and the standard formulation with varying pro- 
portions of it added was examined by this technique. It was found that at 
least ten parts by weight of pure ettringite had to be added to the stan- 
dard mixtures before the peak at 9.1° 2$ was visible. This would account 
for the lack of the appropriate peak in the x-ray diffraction spectra of 
the cured mixtures . 

A specimen of the standard mixture was allowed to cure for approxi- 
mately nine months. At this age, the XRD pattern shown in Figure 28 was 
obtained. At this point it was obvious that ettrigite was present in the 
spectrum, indicating substantial amounts of it in the mixture. Another 
interesting aspect of the pattern was that gypsum was still found to be 
present. The SEM micrograph, Figure 37 (page 125), indicated a continu- 
ous mass of reaction product. Some roundness, where fly ash spheres were 
present, was obvious. However, the spaces between these spheres were com- 
pletely filled with the new product phase. 

With regard to the higher sulfate formulation, very few differences 
were noted when compared to the standard formulation. This would be expected 
since excess gypsum was found in the standard mixture even after nine months. 
The x-ray diffraction patterns were similar, with ettringite not being pres- 
ent until the last sample examined at eleven months. 



29 



The formulation prepared with calcium sulfite was only examined until 
91 days. Strength studies had indicated that by this time calcium sulfite 
gave strengths comparable to calcium sulfate formulations. The x-ray dif- 
fraction patterns indicated that calcium sulfite was present at 7 and 28 
days, but by 91 days had all been consumed. Some peaks corresponding to 
gypsum were present even at 91 days. However, gypsum was present as an 
impurity in the original calcium sulfite sample. Very little compound 
development was obvious by SEM after 7 days. However, the same situation 
was true for formulations with calcium sulfate. The 91-day sample is shown 
in Figure 38 (page 126) . The same type of features were present as with 
the gypsum formulations. Crystal growth was apparent on the particle sur- 
faces. These crystals grew into the pores and intertwined to form a more 
solid structure. Identification of this phase was not possible. If it 
were ettringite, whether or not it formed through the calcium sulfite was 
also not pursued. 

The slump and extrudable consistency were identical formulations of 
the dry ingredients. The results obtained from them were identical though 
differences in reaction rates might be expected with the different water 
contents. The main conclusions for these samples were that the reactions 
proceeded similarly to compacted samples. However, due to the larger pore 
sizes and higher water content, longer cyrstals grew and in the initial 
stages, less particle coalescence occurred. 

Figure 39 (page 127) presents a picture of the slump consistency sample 
after 28 days. When compared to the compacted specimens, it could be seen 
that there was considerably more new crystal formation in the slump sample. 
Also, the crystals appeared to be longer and thinner. In a mixture at 
slump consistency, the fly ash particles were not in as close proximity as 
in the compacted specimens. This gave more room for crystals to grow undis- 
turbed. The fact that there was more reaction product might be due, in part, 
to the fact that there was more lime in these mixtures. Yet, by 28 days, 
no lime was present as testified by the lack of any x-ray diffraction pattern. 

At longer time periods (greater than 6 months) significant differences 
between the high and low water formulations were noted both in the SEM and 

30 



XRD. In Figure 40 (page 128), the areas between the fly ash spheres were 
seen to be totally filled with reaction product. No needle shaped crystals 
were noted. The fly ash spheres themselves were still spherical and when 
viewed under high magnification, did not reveal any surface pitting. The 
XRD pattern, Figure 41 (page 129) quite obviously revealed a peak at 9.3° 
20. This would correspond to either ettringite or tetracalcium aluminate 
monosulfate-14 hydrate. In fact, for all samples at a slump or extrudable 
consistency aged greater than six months, a peak in the region of 9.2-9.3° 
2Q was present. 

Returning to Figure ^0, the extensive infiltration of material into 
the pores to form a more compact arrangement should have great influence on 
strength properties. When freshly mixed and molded, the product could be 
thought of as a packing together of spheres. This would not be very stable 
since there is minimal particle contact and indeed the strengths were low. 
However, after six months, the mass appeared to consist of a solid phase 
interspersed with fly ash spheres. The compressive strength data revealed 
the added stability from the new compound formation. Table 29 presents the 
strength obtained from the compound development specimens. Each value 
represents only one specimen. As can be seen, by six months the extrudable 
and slump consistency specimens had developed as much strength as the stan- 
dard mixture had by nine months. Even though the slump and extruded sample 
had greater void volume than the compacted specimen, the filling in of 
these pores by reaction product to form a solid mass produced similar type 
materials for these longer time periods. 

Two hypotheses could be proposed for the strength results found. One 
is that due to the greater amount of lime in the slump and extruded formu- 
lations, more reaction product was formed. The other explanation is that 
the compacted specimens did not hydrate completely. 

In order to further identify the product formed, energy dispersive 
x-ray analysis was performed on selected samples. Mixtures were examined 
that had cured at least 91 days and would allow focusing of the electron 
beam on reaction product only. Results from these studies were inconclu- 
sive. Almost all spectra indicated the presence of calcium, sulfur, 



31 



aluminum and silicon. The fact that sulfur was found showed that the 
reaction product was composed either entirely or partly of ettringite or 
the low sulfate form, since spectra were obtained from areas where gypsum 
was not present. However, the presence of silicon was disturbing. This 
could be due to the experimental procedure. The electron beam does pene- 
trate into the specimen. Therefore, the silicon peak could be coming from 
the fly ash. Also, geometry plays an important role in this type of analysis 
and it was very difficult to find a spot on the sample that was flat and in 
direct line between the electron beam and the detector. Attempts were made 
to isolate crystals by gently mulling a sample and examining the resultant 
powder. However, it was not possible to obtain any specimens without fly 
ash present. It is also quite likely that silicon was present as a calcium 
silicate hydrate gel which was interspersed within the crystal structure of 
the visibly identified reaction product. 

Calcium silicate hydrate gel has been reported as the major product 
of lime- fly ash reactions. Therefore, its presence in lime- fly ash- sulfate 
mixtures would be expected. In an attempt to identify it, a few specimens 
were examined using the energy dispersive x-ray analysis technique. The 
rate of formation of calcium silicate hydrate is slower than that of calcium 
sulfoaluminate and if a calcium silicate hydrate gel was formed in these 
mixtures, it should be more abundant in areas nearer the fly ash spheres. 
To check this hypothesis, a series of x-ray analyses were made in areas 
where a fly ash sphere had been present. Figure 42 represents such an 
area. In these investigations, an accelerating voltage of 9 kV was used to 
minimize beam penetration. Analyses were run in the center of the hole, 
on the edge of the rim and two spots further out into the crystal mass. 
If calcium silicate hydrate gel was being formed, the silicon content at 
the first two spots should be higher than in the crystal mass. The results 
from this experiment were again inconclusive due to operating difficulties. 
Sample charging was encountered which made electron beam pinpointing diffi- 
cult. Also, since the surface was not flat, such geometric properties as 
shielding and x-ray detecting efficiency varied from spot to spot. There- 
fore, using this technique, we were not able to establish the presence of 
the calcium silicate hydrate phase. 

32 



In conclusion, the formation of a new phase consisting mainly of a 
calcium sulfoaluminate compound has been demonstrated for these mixtures. 
Crystal growth begins in a very short time span and especially for the 
slump and extruded specimens, caused significant strength increases for 
at least six months. DSC indicated that a new species was present within 
one week and continued to be formed during the length of time that samples 
were examined. The new phase that formed was able to fill the majority of 
the pore structure and become the predominant structure of the mixtures. 
X-ray diffraction indicated that the lime disappeared rapidly, usually 
within 14 to 28 days while the gypsum was consumed more slowly and was 
still present in the compacted specimen after nine months. The only new 
phase identified in compacted specimens was ettringite and this was after 
many months of curing. Attempts to identify calcium silicate hydrate gel 
were not successful. 

Use of Waste Sulfates in Lime-Fly Ash-Sulfate-Water Systems 

Characterization of Waste Sulfate Materials 

Using the information gained from the studies with pure gypsum, formu- 
lations were examined with actual waste sulfates. Eight sources of waste 
material were obtained representing the categories: 1) neutralized acid mine 
drainage, 2) industrial wastes, and 3) gas scrubber waste. Upon receipt, 
the materials were stirred until uniform in composition and samples removed 
for analysis. They were examined for solids content, loss on ignition at 
950°C, pH and chemical constituents. The sources of materials and their 
properties are reported in Tables 30 and 31 (pages 172 and 173). 

All the waste samples were obtained from disposal ponds except the acid 
mine drainage sample from EPA, which was a material they prepared in their 
laboratory by limestone neutralization of actual acid mine drainage. All 
three neutralized acid mine drainage samples had a low solids content. The 
precipitate itself was reddish-brown, indicative of ferric hydroxide, and 
gelatinous, caused mainly by the iron and aluminum hydroxides, and was very 
hard to dewater by centrifugation. The x-ray diffraction patterns of the 
solid obtained after drying at 35 °C in vacuo indicated gypsum as being 



33 



the main product in each waste. W 1 gave a poor spectrum and was mainly 
amorphous. Calcite was also identified. W„ gave stronger gypsum peaks than 
W., with no extraneous crystalline material. W~ gave the strongest gypsum 
peaks and appeared to be the purest of the materials. 

Titangypsum is obtained from the neutralization reaction of waste sul- 
furic acid in making TiO~ from ilmenite. The pH of a 10 percent slurry of 
the waste in water was low which meant that neutralization was not complete. 
According to the XRD pattern, the material consisted primarily of well 
crystallized gypsum with the major impurity being titanium dioxide (peaks 
at 25.4°, 27.6°, and 54.3°). 

The waste from hydrofluoric acid production was the only material 
received as a solid. It is produced as a by-product when sulfuric acid is 
reacted with fluorspar, CaF 9 , to form hydrofluoric acid. Before use, it 
was necessary to crush the material. Our procedure was to use a Wiley mill 
and to grind it to pass a 0.5 mm screen. Along with gypsum, calcium fluo- 
ride and anhydrous calcium sulfate were identified in the x-ray diffraction 
pattern of W_. 

The gray color of the gas scrubber from Kansas Power and Light Co. was 
caused by fly ash that was contained in the slurry. The high pH of the 
material indicated excess lime was present. Therefore, the total waste con- 
sisted of gypsum, fly ash, lime, and water; in other words, a reactive mix- 
ture. Identified in the diffraction pattern of this material were gypsum, 
quartz (from the fly ash) and a peak at 9.2° 20 indicative of ettringite. 
The gypsum peaks were relatively weak compared to other waste sources. It 
was not possible to ascertain the length of time that the material had been 
stored in the pond at the power plant. We used the material immediately 
upon receipt. Therefore, the results were all for the same material, but 
might vary significantly if fresh material were used. 

The neutralized steel pickling liquor was a reddish color, gelatinous 
material and similar in appearance to the neutralized acid mine drainage. 
The sulfate content of this waste, W 7 , was found to be very low and this was 
verified by the fact that calcite and not gypsum was the major crystalline 
constituent fround by x-ray diffraction. 



34 



The last material, W , was another sample of flue gas desulfurization 

o 

sludge. As with the other gas scrubber sludge, it contained some fly ash. 
However, the sulfur in W ft was present mainly as calcium sulfite rather than 
calcium sulfate. As with W, , all the specimens were prepared at the same 
time in order to minimize differences that would result from using a sample 
of the sludge at a different age that would have undergone more "self re- 



Strength Studies of Waste Sulfate Mixtures 

To determine the reactivity of these materials in relation to pure 
calcium sulfate, compressive strength studies were performed. Formulations 
were limited due to the high water content in most of the sludges. In fact, 
W„ had to be eliminated from evaluation since it contained only four percent 
solids. In most cases reported in this work, the highest sulfate content 
listed refers to a sample prepared where the total water content was derived 
from the sludge. For two of the materials, W, and W_, the solids were con- 
centrated by centrifuging the sample. It was felt that this -would be the 
best method to concentrate the sludges without changing their chemical or 
physical composition. After one hour of centrifuging with a laboratory 
centrifuge, W, increased in solids content from 8 to 14 percent, while for 
\J. the increase was from 17 to 29 percent. 

Table 32 (page 174) gives the data for samples prepared using neutra- 
lized acid mine drainage. The maximum solids content possible with the cen- 
trifuged sample of W, was 3.6 percent, while with the waste as received it 
was 1.9 percent. When compared to a similar mixture containing no waste 
with the same lime content, very little difference in strength was noted. 
However, the density was seen to be lower for the waste containing samples. 
With the other material, W-, higher solids contents were possible and a set 
of compacted specimens was prepared where the lime content was kept constant 
and the waste content was increased from 3.1 to 7.8 percent solids. It was 
observed that as the waste solids content increased the dry density of the 
samples decreased, as would be expected when fly ash was replaced by a 
material containing quantities of aluminum and iron hydroxide gels. The 
seven day strengths were found to decrease with increasing waste sulfate 

35 



content. This would be a reflection of the dry density dependence already 
noted. The magnitude of the seven day strengths are worthy of note, since 
they showed that in all but one case, the waste sulfate did enhance this 
property when compared to the mixture without any gypsum. When compared 
to the standard mixture containing 4.7 percent calcitic lime, 9.3 percent 

gypsum and 86 percent Ft. Martin fly ash which had a seven day strength of 

2 
545 p.s.i. (3,755 kN/m ), the neutralized acid mine drainage compared quite 

favorably. The 28 day strengths, though higher than the mixture without 

2 
gypsum, was much less than the 2000 p.s.i. (13,780 kN/m ) obtained with the » 

standard formulation. When the effects of impurities on the standard formu- 
lation were examined, Table 27, the mixture prepared by neutralizing ferric 

nitrate with sodium carbonate exhibited 7 and 28 day strengths of 355 and 

2 
475 p.s.i. (2,446 and 3,273 kN/m ) respectively. The ratio of 28 day strength 

to 7 days strength from this study, 1.3, was similar to the data in Table 32 

which gave ratios from 1.3 to 1.9, indicating that the effect of the aluminum 

and iron hydroxides were present with the acid mine drainage waste. For the 

standard mixture the ratio was 3.8. 

The other entries in Table 32 were samples prepared at extruded or 
slump consistency. For the extruded samples the lime content was varied at 
constant waste sulfate content and very little variation in strength resulted. 
Surprisingly, the slump mixtures gave higher strengths at the longer time 
curing periods. 

Table 33 (page 175) gives the results using the industrial wastes. The 
titangypsum, W, , contained a higher solids content than the acid mine drainage 
samples so that higher waste levels could be examined. The other ingredients 
and formulation chosen was based on the standard formulation. Again, the 

dry densities were lower with the sludge- like ^aste when compared to pure 

2 

gypsum. The 7 day strength of 580 p.s.i. (3,996 kN/m ) compared quite favor- 

2 

ably with the 545 p.s.i. (3,755 kN/m ) strength developed with pure gypsum. 

2 
The 28 day strengths of 1000 p.s.i. (6,890 kN/m ) were better than the acid 

mine drainage waste but only half the magnitude of the standard formulation. 

This waste was also examined at a slump consistency. Previous results with 



36 



pure gypsum were used in determining a realistic formulation. The 28 day 

2 
strength of 1145 p.s.i. (7,889 kN/m ) obtained was equal to the highest 

strength obtained with these or any other limes and fly ashes at an extrudable 

or slump consistency when compared to Tables 17 and 18. The 91 day strength 

of 1275 p.s.i. (8,785 kN/m ) indicated very little change had occurred over 

this longer time period. 

The hydrofluoric acid by-product, W,., being a solid material, allowed 
more latitude in formulation. It was examined in combination with the dolo- 
mitic monohydrated lime and Amax fly ash. With 3.2 percent lime, 92 percent 

fly ash, and 4.8 percent gypsum the 7 day strength was 620 p.s.i. (4,272 

2 2 

kN/m ) and the 28 day strength was 1130 p.s.i. (7,786 kN/m ). This same 

formulation with W replacing gypsum had a 7 day strength of only 360 p.s.i. 

2 2 

(2,480 kN/m ) but a 28 day strength of 1150 p.s.i. (7,924 kN/m ) , the same 

as mixtures prepared with pure gypsum. Increasing the waste sulfate content 
caused an increase in the 7 day strength up to 20 percent solids. For the 
pure system, Table 19, this type of behavior was noted up to around 8.4 per- 
cent gypsum. For the 28 day strengths, the reference formulation was found 
to maximize at 10 percent gypsum. With W,., even at 20 and 25 percent solids, 
the strength was still slightly increasing. At an extruded and slump consis- 
tency, W_ behaved as gypsum, producing strengths near 1000 p.s.i. (6,890 

2 2 

kN/m ) at 28 days and 1500 p.s.i. (10,335 kN/m ) by 91 days. 

Neutralized steel pickling liquor, W 7 » wa s the other industrial waste 
examined. Analysis of the waste indicated that it contained very little 
gypsum. Compacted specimens were prepared at near maximum sludge content 
which corresponded to five percent solids in the final mixture. The average 
dry densities of the specimens were found to be low, indicative of the hyrox- 
ide gels in the waste. A series of experiments were performed where the 
lime content of the mixture was varied. The data indicated that very little 
strength variation occurred within this series. These strengths were of 
the magnitude that would be expected from lime- fly ash mixtures of these 
specific lime and fly ash combinations. Thus this waste did not contribute 
to increased strength development. At a slump consistency this material also 
performed poorly. After 7 days the specimens were still wet and poured out 

37 



of the mold. After 28 days the specimens were drier, but still were not 
stronger than an uncured, compacted specimen. 

The last major waste category examined was gas scrubber waste. The 

material from Kansas Power and Light Co., W,, was examined in combination 

with Ft. Martin fly ash and calcitic lime, which were held at a constant 

ratio of 17. The data in Table 34 (page 176) showed that the waste did 

influence the strength of the final mixtures. This was especially obvious 

from the 7 day strengths. Here, increased waste content coupled with 

slightly decreased lime addition levels caused an increase in strength. 

2 
A value of 545 p.s.i. (3,755 kN/m ) was obtained after 7 days with 4.7 

percent lime and 9.3 percent pure gypsum. The 28 day strengths did not 
exhibit much variation within this series. Also the values were only 
about half that obtained with the pure gypsum system. However, it must 
be remembered that the x-ray diffraction pattern of the waste itself indi- 
cated that significant pre-reaction of the waste had occurred. 

The other gas scrubber waste, W , was examined more extensively. Here, 

o 

the sulfur was present as calcium sulfite. The x-ray diffraction pattern 
had indicated that when we received the waste, no appreciable oxidation to 
calcium sulfate had occurred. This material was examined in combination 
with Amax fly ash. When the waste content was increased from 3.0 to 16.7 
percent solids at a constant lime level of 7.0 percent, a decrease in 7 day 
strength was found. This was different behavior than noted with pure gypsum, 
where a maximum in strength was found with equal weight percentages of lime 
and gypsum. The 28 day strengths were found to exhibit very little vari- 
ation, even though the waste content was increased from 3.0 to 16.7 percent 

2 
of the dry materials. The value of 1200 p.s.i. (8,268 kN/m ) for the average 

28 day strength was quite respectable when compared to others obtained with 
Amax fly ash and pure gypsum or calcium sulfite. 

As with all the wastes that were of sludge consistency, compacted 
strength samples were found not to be of uniform composition. Although mix- 
tures of the sludge, lime and fly ash appeared uniform, when cut in half, 
pockets of unmixed sludge were visible. To see if this was affecting 
strength development, alternate mixing procedures were examined. In the 

38 



first such entry in Table 34, the waste and extra water were blended in the 
mixing bowl. Next the fly ash was slowly blended in and finally the lime was 
added. The mixture was then stirred for another two minutes. For the other 
marked entry, the lime and fly ash were pre-blended and then slowly added 
to the mixer which already contained the sludge and water. In both cases, 
the more intimate mixing produced higher 7 and 28 day strengths. 

The last three entries in Table 34 represent an evaluation of lime con- 
tent. With a waste level of 12 percent solids in the final dry mixture, it 
was found that the 7 day strength increased with increased lime content. 
This was the behavior that would be expected based on the waste sulfate con- 
tent. The 28 day strength also increased appreciably with lime content. The 

most important difference here was between one and three percent lime, where 

2 
the strength quadrupled from 300 to 1200 p. s .i. (2,067-8,268 kN/m ). 

Engineering Evaluation 

Six lime-fly ash-sulfate formulations were selected for further engi- 
neering evaluation. These formulations are shown in Table 35 (page 177) . 

The first formulation was the model system employing pure gypsum. 
This formulation was chosen to provide a check of sample preparation and 
certain testing procedures for the two laboratories (UVa and GRI) . More- 
over, the results of tests on this formulation provided a standard for com- 
paring the five waste sulfate formulations. 

The tests which were employed to determine and evaluate the engineering 
properties of each formulation are shown in Table 36 (page 178). Standard 
ASTM tests were used, where applicable. Triplicate samples were prepared, 
sealed in plastic bags, stored in a humid room at 73° ±2°F (23°C) and sub- 
sequently tested. The compressive strength of those samples which with- 
stood the twelve cycles of freeze-thaw and wet-dry testing was determined. 
Falling head permeability tests were run on compacted samples to determine 
the coefficient of permeability. Leachate obtained from each sample during 
the permeability test was collected for chemical analysis. Two fractions 
of leachate were obtained, one being the first 150 ml to pass through the 
permeability sample and another 150 ml specimen after the sample had been 

39 



saturated with de-aired water and the permeability test run. Therefore, 
both an initial outflow and a longer term leachate sample were studied. 
Background samples of water which had passed through the clean and empty 
permeameter were also obtained. The leachate samples were all analyzed 
for alkalinity, calcium hardness, total hardness and sulfate. Specially 
selected samples were also analyzed for iron and fluoride. 

Determination of Engineering Properties 

The results of unconfined compression, split cylinder (tension), per- 
meability and California Bearing Ratio tests on all formulations are shown 
in Table 37 (page 179) . 

The unconfined compressive strength of all formulations seems to be 
quite good although the waste sulfate formulations were not as strong as 
the "standard" gypsum formulation. Compressive strength generally increased 
with curing time. The same observation can be made in the case of split 
cylinder (tension) tests. 

The California Bearing Ratio (CBR) was quite high for all formulations-- 
the standard gypsum having the highest CBR. In all cases, the CBR for these 
formulations exceeded that of the well graded crushed stone CBR standard. 

The permeability of all formulations was quite low, all formulations 
Jbeing essentially impervious. For purposes of comparison the permeability 
of these lime- fly ash- sulfate formulations was similar to that of a fine 
sandy or silty clay. The increase in permeability exhibited by some 28-day 
cured specimens is believed to have resulted from sample expansion during 
the 7- and 28-day curing periods. 

Shown in Table 38 are the average dry unit weights and water contents 
of samples subjected to strength (compression and tension), permeability 
and CBR tests. The compacted dry unit weights of all formulations studied 
were considerably lower than most soils currently used in highway construc- 
tion. This could prove to be a real advantage where lightweight materials 
are needed in crossing soft compressible deposits on fill. Settlement and 
the occurrence of a shearing displacement of the soft underlying should be 
lessened with the use of lime- fly ash-sulfate embankments. 

40 



Durability Studies 

The results of freeze-thaw tests on compacted and cured samples are 
shown in Table 39 (page 181). In the first column of Table 39 are the 
results of compressive strength tests upon samples which were prepared at 
the same time and in the same manner as the regular freeze-thaw samples 
but were cured in a humid room at 73°F (23°C) for 15 days. This 15-day 
period of curing was arbitrarily chosen to obtain a strength standard for 
comparison with similar specimens cured for 7 days followed by twelve 
cycles of freezing and thawing. 

With the exception of the standard gypsum formulation, most samples 
did not survive 12 cycles of freezing and thawing whether brushed or un- 
brushed. The loss of solids from brushed samples as shown in Table 39 
was considered excessive. The volume change for unbrushed samples after 
curing and then cyclic freezing and thawing are also shown in Table 39. 

Shown in Figure 43 (page 131) is a photograph of Acid Mine Drainage 
(W~) samples after three cycles of freezing and thawing. 

On the basis of these freeze-thaw tests, it would appear that curing 
at 73°F (23°C) for a period of 7 days, or less, is not normally sufficient 
to develop the required resistance to freezing and thawing for many lime- 
fly ash-sulfate formulations. 

The results of wet-dry tests are shown in Table 40 (page 182) . In the 
second column of this table the results of compressive strength tests upon 
compacted and 15-day cured specimens have been reproduced from the table 
(Table 39) for freeze-thaw tests. The break-up, loss of solids and volume 
change for the wet-dry samples which had been cured for 7 days were con- 
siderably less than in the freeze thaw tests. Therefore, the cyclic wetting 
and drying of lime- fly ash-sulfate formulations does not appear to be as 
detrimental as that of cyclic freezing and thawing. 

In order to determine if the freeze-thaw and wet-dry durability of 
lime- fly ash-sulfate formulations might be improved, a few special tests 
were conducted. These were as follows: The scrubber sludge (W„) formula- 
tion was selected and compacted specimens of this material were cured in 

41 



a humid room at 73°F (23°C) for 28, rather than 7 days. One half of one 

percent of calcium chloride was added to one group of these compacted 

freeze-thaw specimens. In another special test, freeze-thaw samples were 

prepared from a slump mix of the scrubber sludge (W Q ) formulation. The 

o 

results of these special tests are shown in Table 41 (page 183). 

Shown in Figure 44 (a) are unbrushed, freeze-thaw samples of the 
scrubber sludge (W ft ) formulation after a 28-day curing period and 14 cycles 
of freeze-thaw. In Figure 44 are shown similar 28-day cured samples of 
the same scrubber sludge formulation, with 1/2 percent of the calcium 
chloride added, which had been subjected to 12 cycles of freeze-thaw. 

On the basis of a limited number of tests on specimens of the W_ 

o 

formulation, it was apparent that a 28-day cure period improved the freez- 
thaw and wet-dry performance of this formulation in comparison to the 7-day 
cure period. The addition of 1/2 percent of calcium chloride did not appear 
to improve the freeze-thaw performance when compared with similar 28-day 
cured samples without the calcium chloride. 



As a result of the engineering tests which were performed upon six 
lime-fly ash-sulfate formulations, the following conclusions appear justi- 
fied. 

1. Properly proportioned, compacted and cured lime- fly ash-sulfate 
mixtures produce a strong, stiff material which may be used in certain road 
building operations such as embankments, sub-grades, sub-bases and bases 
for pavements. 

2. Durability of these mixtures, as measured by freeze-thaw and wet- 
dry tests, was insufficient where only 7 days of curing at 73°F (23°C) was 
employed. A 28-day curing period at 73°F (23°C) produced much better dura- 
bility in the one formulation studied. The durability of compacted lime- fly 
ash sulfate mixtures for pavement components will therefore need to be 
carefully considered in cold climates. 

3. The compacted lime- fly ash-sulfate mixtures studied were quite 
impervious indicating that selected formulations might be employed in dikes, 
lagoons, and levees. 



42 



4. Compacted lime- fly ash-sulfate formulations are normally lighter 
in weight than most compacted soils. This could prove to be a real advan- 
tage where soft compressible ground is to be crossed with an embankment. 

Leachate Analysis 

Outflow from the permeability tests was collected and analyzed for 
chemical constituents. All samples were measured for pH, "P" alkalinity, 
"T" alkalinity, calcium hardness, total hardness, fluoride and sulfate, 
while aluminum and iron were determined for certain formulations. 

The pH of the samples were measured with a glass electrode. Alkalin- 
ity, which has little or no relation to pH, refers to the amount of various 
alkalies in the water which are capable of neutralizing acids. "P" alka- 
linity was determined by titrating with a standard acid solution using 
phenolphthalein indicator. The titration end point was at pH 8.3. This 
procedure measures the hydroxide content and half the carbonate present. 
"T" alkalinity or total alkalinity from hydroxides, carbonate bicarbonates, 
etc., was obtained by titrating with the standard acid solution to the 
methyl orange end point at pH 4.5 to 5.1. 

Calcium hardness is a measure of the calcium ion concentration present. 
Total hardness indicates the combined calcium and magnesium ion content. 
Both were determined by complexiometric titration, using different indica- 
tors. Sulfate ion was determined by the turbidimetric method. The only 
source of sulfate in the leachate was the waste sulfate in the mixtures, 
so this value gave a measure of the reactivity of the mixture. Fluoride was 
determined using a fluoride sensitive electrode. It was included since the 
sulfate waste was from hydrofluoric acid production, and some residual cal- 
cium fluoride was known to be in the waste. The metal ions, aluminum and 
iron were analyzed by atomic absorption spectrophotometry. 

Table 42 (page 184) presents the data from the permeability tests listed 
in Tables 35 and 37. All effluents had an alkaline pH as would be expected 
from lime containing specimens. The initial outflows (the first 150 ml from 
each permeability test) were usually higher in ions removed than the final 
sample which was taken after the permeability test was completed. The final 
entries in Table 42 are the data that represent the effect of water effluent 

43 



volume on leachability. Here it was found that the concentration of salts 
removed from the specimens decreased to a low level. Materials such as 
gypsum and lime that were initially added are partially soluble in water and 
would be easily removed by dissolution. This would explain their high, 
initial effluent ion levels. 

Curing time was also seen to effect leachate levels in many cases. 
Samples cured for 28 days had less soluble material present than samples 
cured for 7 days. This would indicate that the lime and gypsum had under- 
gone reaction to form an insoluble material. Though the leachate level 
might be considered to be high, especially for the initial outflow, when 
coupled with the permeability of this material it indicated that very little 
groundwater infiltration would occur. 



Study of Lime-Fly Ash-Sulfate Systems as Aggregate for Portland Gement and 
Bituminous Concrete 



A series of laboratory investigations were conducted to evaluate the 
performance of the waste materials as aggregate particles in portland cement 
and asphaltic concrete mixtures. Aggregates were prepared by two different 
processes identified as "cast" and "extruded," and from three different com- 
binations of waste products. These materials were subsequently crushed, 
graded and used as aggregate in concrete mixtures. Compressive and tensile 
strength properties and freeze-thaw durability characteristics were deter- 
mined for a number of different concrete mixtures. In addition, sulfate 
soundness, freeze-thaw durability, and abrasion resistance tests were con- 
ducted on the aggregates themselves. 

Throughout the concrete aggregate investigations, studies were made 
beyond standard acceptance-test procedures to ascertain conditions by which 
the properties of the aggregates might be enhanced and the waste materials 
therefore used advantageiously for engineering applications. In order to 
achieve this goal, some of the investigative procedures used in the study 
were not strictly in accordance with the provisions set forth in ASTM and 
AASHTO Standards. However, a number of standard test procedures were con- 
ducted to determine material properties which may be compared with specifi- 
cations for acceptable concrete aggregates. 

44 



In general, the portland cement concrete test results indicated accept- 
able strength values for specialized application but unacceptable durability 
factors for exposure to cyclic freezing and thawing environments. Similarly, 
the asphaltic concrete test results indicated acceptable mechanical proper- 
ties but unusually high bituminous binder requirements. 

Materials and Aggregate Preparation 

Component Materials The constituent materials used for the cast and ex- 
truded aggregate formulations were determined from optimization studies. 
The various solid components were combined by weight percent as follows: 



1. Cast aggregate: Lime A, 



8.0% 



Fly Ash C 3 - 80.0% 

Calcium Sulfate W - 12.0% 

Added tap water as a percent of 

the total weight of solids - 40.0% 

Trial mixtures containing water contents of 35 and 33 percent water were 
also prepared to determine the lowest water content which would permit 
adequate consolidation of the plastic mixture after placement in the mold. 
The lower water-content mixtures were rejected for aggregate production 
because it was impossible to consolidate specimens for strength tests which 
did not contain large air voids. 

2. Extruded aggregate, formula 1: 

Lime A.. 
Fly Ash C, 
Sulfate W (Sludge) 
Extruded aggregate, formula 2: 
Lime A_ 
Fly Ash C 
Sulfate W (Sludge) 

The sludge (W sulfate) contained a sufficient amount of water for the 
desired consistency of the mixture so no tap water was added. The corres- 
ponding dry weights of the solids in formulas 1 and 2 were: 

45 



7 


.5% 


61 


.9% 


30 


.5% 


7 


.5% 


61 


.9% 


30 


,5% 



Lime - 10 . 1% 

Fly Ash - 83.0% 

Sludge Solids - 6.9% 

The resulting moisture content was 30% of the weight of the dry solids. 

Both of the aggregate formulations produced by the extrusion process 
were soft and unusable after 28 days of moist curing at 72°F (22°C). Sub- 
sequent curing at 120°F (40.9°C) for 14 days improved the hardness and 
strength of the formulation 1 aggregate, but did not improve the character- 
istics of formulation 2. All concrete mixtures were therefore made with 
the formulation 1 aggregate. 

Aggregate Manufacture and Gradation 

Cast aggregate (Prepared in the laboratory at the University of Virginia 
(UVa)). Solid components were blended dry in an orbital mixer (Champion 
Model AS80) and then water was added to produce a batch weight of 56 pounds 
(25 kg) . Mixing was continued for several minutes until a uniform consis- 
tency was obtained. The entire batch was then placed in a steel mold, 
6x6x36 inches (15.2x15.2x91 cm) and vibrated for five minutes on a table 
with a constant frequency of 3600 cpm. After vibrating, the molds were 
placed in a fog room for curing at a temperature of 72 °F (22 °C) in an atmo- 
sphere of 100 percent relative humidity (RH) for a period of 28 days, A 
total of 758 pounds (345 kg) of material was mixed and molded. In addition 
to the large blocks, compressive test specimens, 2x2-inch (5.1x5.1 cm) cubes 
and 2x4- inch (5.1x10.2 cm) cylinders were molded. The cast material was 
subsequently crushed and graded for use as concrete aggregate. 

Extruded aggregate (Prepared at Gillette Research Institute) The sulfate 
sludge was placed in the bowl of the mixer and the paddle was rotated at 
a slow speed. The fly ash and then the lime was added to the sludge in 
increments to insure complete mixing of the components. Stirring was con- 
tinued for 10 minutes after all of the materials were in the bowl. This 
procedure produced a material with a consistency which was sufficiently 
plastic and cohesive to mold but did not dewater in the die nor "bleed" 
when extruded. The plastic material was then placed in the extruder and 



46 



forced through circular-shaped dies to form long rods on aluminum sheets. 
Some of the rods were handcut with a spatula into lengths approximately equal 
to the diameter of the rod. Diameters of 3/8, 1/2 and 3/4 inches (0.95, 
1.27 and 1.90 cm) were extruded for both formulas 1 and 2 to produce a total 
of approximately 400 pounds (182 kg) of material. All of the extruded mate- 
rial was placed in moisture-proof containers for transport to UVa and storage 
in the fog curing room for a period of 28 days. Following the 72 °F (22 °C) 
temperature curing, the aggregate was postcured at 120°F (49°C) and 100 per- 
cent RH for a period of 14 days. 

After curing, the block and extruded materials were crushed separately 
as required in an oscillating- jaw type of rock crusher. The crushed material 
was passed through vibrating sieves to separate particle sizes for blending 
into the following gradations shown as weight percent retained on the indi- 
cated sieves: 



Sieve 


Portlai 


id Cement Concrete 


Bituminous Concrete 


Number 


Fine 




Coarse 




Blend 




A 


B 


C 




3/4" 





3 











1/2" 





30 


5 








3/8" 





30 


40 


8 


10 


#4 


3 


35 


48 


72 


30 


#8 


17 


2 


7 


20 


15 


#16 


18 








11 


#30 


21 








11 


#50 


21 








8 


#100 


14 








9 


#200 


6 








6 



The coarse aggregate gradations A, B and C corresponded to the 
size designations 67, 7 and 8 of AASHTO Specification M-43 respectively. 
The fine aggregate gradation corresponded to AASHTO Specifications M-6 and 
M-195. The asphaltic gradation conformed to Specification S-5 of the Vir- 
ginial Department of Highways and Transportation for bituminous concrete. 



47 



Considerable waste in the form of dust and particles finer than the 
#8 sieve occurred during the crushing operation of the cast material. Be- 
cause of this observation, a study was made of the losses incurred as the 
extruded material was crushed and handled. As described previously, the 
"cut" material was chopped into lengths equal to the nominal diameter as 
it was discharged from the extruding machine, whereas a certain amount of 
the material was not cut into specified lengths before curing and was in 
the form of "rods." It was proposed that this procedure be used to deter- 
mine if the properties of the aggregate were affected by cutting to the 
proper size before curing. However, an evaluation of property differences 
was not made. Breakage of the rod material and to a lesser extent, the 
cut material, resulted from handling. Initial sieving of the "as received" 
extruded aggregate indicated the following distribution of particle sizes 
for the 3/4 inch top size in percent by weight retained. 

Sieve Cut Rod 



3/4" 




51 


32 


1/2" 




23 


7 


3/8" 




10 


40 


#4 




4 


6 


#8 




1 


2 


Passing 


#8 


10 


13 



It is interesting to note that 10 percent of the cut material and 13 
percent of the rod material were too small for use in the coarse aggregate 
gradation and therefore were wasted. Additional fines were produced when 
the larger sizes were crushed to provide the #4 and #8 sizes required. 
From a total of 141 pounds (64 kg) of material which was crushed from the 
1/2-inch (1.27 cm) and larger sizes, 49 pounds (22 kg), or 34 percent was 
wasted as sub-#8 size. When all operations of handling, crushing and siev- 
ing were considered, it was noted that 74 pounds (34 kg) out of a total of 
222 pounds (101 kg), or 33 percent of the original aggregate was wasted. 
Unless the waste fines could be recycled or used in some way, much of the 
advantage of utilizing the synthetic aggregate for construction purposes 



48 



would be lost in the extrusion method of manufacture. Problems associated 
with incorporating the fine material in concrete mixtures are discussed in 
a later topic. 

Aggregate Properties 

Several standard tests were conducted to determine properties of funda- 
mental interest. These are indicated by AASHTO designation as follows: 

1. Specific Gravity and Absorption of Fine Aggregates, T84. 

2. Unit Weight of Aggregate, T19. 

3. Soundness of Aggregates by Use of Sodium Sulfate or Magnesium 
Sulfate, T104. 

4. Soundness of Aggregates by Freezing and Thawing, T103, Procedure B. 

5. Resistance to Abrasion of Coarse Aggregate by Use of the Los Angeles 
Machine, T96. 

6. Compressive Strength of Hydraulic- Cement Mortars, T106. (Applicable 
sections were used as a guide) . 

Most of the property determination tests were conducted with the cast 
aggregate because of the availability and accessibility of this material. 
These tests were conducted at the University of Virginia unless otherwise 
noted. However, there was no reason to believe that the extruded aggregate 
would exhibit significantly different properties. The properties of the 
aggregates studied at UVa were compared (see appendix C) with those cited 
by L. John Minnick (8) for synthetic aggregates composed of lime- fly ash- 
sulfate-water mixtures. The properties of the aggregates from the two differ- 
ent sources are considerably different with the UVa source exhibiting inferior 
performance. The test results were as follows: 

1. Specific Gravity: The saturated surface dry (SSD) specific gravity 
was approximately 2.00. The water absorption was approximately 18.5 percent 
of the oven dry weight. These values were the average of two samples of fine 
aggregate gradation. No additional specific gravity determination was made 
for the coarse aggregate gradations. 

2. Unit Weight: The unit weight of the coarse aggregate gradation A 

3 
was 56 pcf (896 kg/m ) . The unit weight of the fine aggregate gradation 

49 



3 

was 61 pcf (976 kg/m ) . These unit weights were close to the values speci- 
fied for lightweight aggregate in AASHTO M-195. Because of this property 
and because of the high absorption value, the material was considered to 
fall within the definition of lightweight aggregate. Guidelines for the 
determination of properties and mixtures proportioning were therefore fol- 
lowed in subsequent evaluations. Blends of coarse (A) and fine aggregates 
were prepared to determine which combinations produced the greatest unit 
weight. Combinations with the fine aggregate fractions ranging from 45 to 

70 percent by weight remained fairly constant with a maximum unit weight of 

3 
approximately 80 pounds per cubic foot (1280 kg/m ). The material was 

slightly drier than the SSD condition when the weight measurements were made. 

3. Sulfate Soundness: Results of the sieve analysis for the sulfate 
soundness test are shown in Table 43 (page 185). This test was conducted 
at the Gillette Research Institute. 

The test was conducted with the specified solution of sodium sulfate 
for one sample of the cast fine aggregate fraction. The sample was alter- 
nately immersed and dried for 5 cycles. Figure 45 (page 134) is a photo- 
graph of a typical aggregate particle following the soundness test. As 
shown, severe splitting and surface pitting of the particles were apparent 
which undoubtedly accounted for the relatively high percentage (27.8) weight 
loss during the test. AASHTO Specifications M-195 and M-80, respectively, 
indicate that an acceptable aggregate shall not have a weighted loss greater 
than 8 percent and 12 percent after 5 cycles of immersion. The aggregate 
therefore failed the durability soundness test of both specifications. 
Freeze-thaw tests were performed subsequently with concrete mixtures to 
confirm the results of this test. A freeze-thaw test in accordance with 
AASHTO T-103 was also performed on the coarse aggregate. 

4. Freeze-thaw Soundness: Results of the sieve analyses for the 
freeze-thaw soundness test are shown in Table 44. The initial sample weight 
consisted of particles passing the 3/8 inch (0.95 cm) and retained on the 
number 4 sieves. The final sample weight was the material retained on a 
number 5 sieve after sieving to constant weight. 

It was intended that 16 cycles of freezing and thawing would be used 
in the test (as suggested by AASHTO T-103), but after 14 cycles, it was 

50 



evident that the aggregate had deteriorated and the test was discontinued. 
Figure 46 shows the condition of the particles after the 12th cycle of freez- 
ing. Duplicate samples were tested simultaneously from the same source of 
cast material. 

5. Abrasion Resistance: The abrasion resistance of the aggregate was 
determined by a Los Angeles test conducted in the Materials Laboratories of 
the Federal Highway Administration. A copy of the test report is appended. 
The results of the tests were 44 percent wear for the cast aggregate and 70 
percent wear for the extruded aggregate. As indicated in the test report, 
a substandard amount of material was available for the tests, so the test 
procedure was modified to accomodate the reduced sample size. The results 
obtained were considered valid for evaluating the property. AASHTO Specifi- 
cation M-195 does not specify a wear resistance property and AASHTO M-80 
specifies that the percentage of wear shall not be more than 40. From this, 
it is evident that neither aggregate sample met the AASHTO M-80 requirement. 

6. Compressive Strength: Samples of the cast aggregate material were 
consolidated in molds for 2x2-inch (5.1x5.1 cm) cubes in the same manner as 
described for the cast aggregate blocks and were produced at the same time 
the blocks were cast. All specimens were moist cured under standard condi- 
tions for the indicated periods of time. Some shear planes developed in the 
28-day old specimens but tensile cracking and crushing failures were also 
observed in the specimens. Results of the compressive strength tests were 

as follows: 

2 2 

Average Stress (lb/in ) Range of Stress (lb/in ) 



Age 


No. 


Specimens 


7 day 




7 


14 day 




8 


28 day 




16 



150 130 to 190 

470 350 to 560 

1170 660 to 1830 

The average compressive stresses shown above compare favorably with 
pilot studies. The range of values were quite large, due, in part, to damage 
to some specimens when they were removed from the molds. 

No compressive strength tests were conducted with the extruded aggre- 
gate. 



51 



Portland Cement Concrete Mixtures Study 

Mixture Parameters and Procedures A total of 42 concrete mixtures were 
prepared with the combinations of cast aggregate series indicated in Table 
45 (page 186 ) and extruded aggregate series indicated in Table 46 (page 
186 ) . A limited supply of aggregates and resources precluded a full fac- 
torial experiment with the indicated parameters. These parameters were 
selected to study principally the effects of the types of aggregate, the 
gradation, and the cement factor upon the compressive and tensile strengths 
of the concrete. Additionally, the effect of moisture in the aggregate 
upon the durability property of the concrete was studied. Comparative data 
were also obtained to ascertain the effects of fly ash-cement paste combi- 
nations and various proportions of synthetic aggregates in the concrete 
mixtures . 

All mixtures were prepared with a Type II cement (Capitol port land 

cement) and an air-entraining agent (Protex) added to the mixing water. 

3 
Batches were proportioned to yield approximately 1/4 cubic foot (0.007 m ) 

and were mixed in a Lancaster counter-current mixer with a 2 cubic foot 

3 
(0.057 m ) capacity but. Specimens for compression and tension tests were 

cast in 3x6-inch (7.6x15.2 cm) cylindrical steel molds and specimens for 
freeze-thaw tests were cast in 3x4xl6-inch (7.6x10.2x40.6 cm) steel molds. 
The molds were vibrated on the table described previously to eliminate 
voids and placed in a fog room at 100% RH for curing at 72°F (22°C). Com- 
pression and freeze-thaw tests were conducted at the end of 7 days and 
28 days of curing. Tension tests were conducted after 28 days of curing. 
All strength tests were performed in a Baldwin- Lima -Hamilton Universal test- 
ing machine with a force capacity of 120,000 pounds (54,500 kg). Water- 
cement ratios for comparable mixtures were held constant as long as the 
resultant consistency permitted satisfactory consolidation of the molded 
test specimens. 

Mixing Procedures and Discussion Because of the known porosity of the 
synthetic aggregates, efforts were made to hold the moisture content at 
the saturated, surface dry (SSD) condition. These efforts were not com- 
pletely successful and undoubtedly accounted for some of the variations in 

52 



the measured slumps of "identical" mixtures. Adjustment were made to the 
computed water requirements for variations in the free moisture condition of 
the natural sand aggregate fractions. These variations were determined with 
a "Speedy" (calcium carbide system) moisture tester. 

The first mixtures prepared consisted wholly of coarse and fine fractions 
of the cast synthetic aggregates in order to maximize the use of the synthetic 
material. Water was added incrementally to predetermined weights of cement 
and aggregates until a desired slump (AASHTO T-119) was obtained. This mix- 
ture appeared quite workable and cohesive as the water was added. However, 
within 15 minutes after adding the water, the mixture appeared to take on a 
false set and was very difficult to mold. The fines (paste) became gummy and 
stuck to hand tools and containers badly. In subsequent mixtures containing 
sand as the fine aggregate, the gummy, sticky consistency of the mixture dis- 
appeared. The influence of the synthetic fine aggregate on the mixture con- 
sistency was explored further by preparing several mixtures with combinations 
of one-half sand and one-half synthetic material. Typically, repetitive slump 
measurements exhibited the following pattern for the all-synthetic mixture: 

(a) immediately after mixing: 10- inch (25.4 cm) slump 

(b) 15 minutes after mixing: 2- inch (5.1 cm) slump 

(c) immediately after remixing for 1 minute: 8-inch (20.3 cm) slump 
The exact nature of this unusual property of the all-synthetic aggregate 

mixture is not known, but is believed to be due to a rapid chemical reaction 
with components of portland cement. A tangential study was conducted to 
substantiate this hypothesis by comparing the flow characteristics of a fine 
aggregate mixture containing 25 percent by weight cement with a mixture con- 
taining no cement. The results of the flow test (AASHTO T-120) are shown 
in Table 47 (page 187) . 

The "initial" values shown were determined immediately after first 
mixing; the "delayed" values were obtained by remixing after the first flow 
test and then leaving the mixture in the flow-test mold for 15 minutes before 
vibrating; and the "remixed" values were obtained by remixing after the 
second flow-test and immediately running a third flow test. The behavior 
of the aggregate- cement mixture was similar to that observed in the slump 

53 



of the concrete mixtures, whereas the delay time did not decrease the work- 
ability of the aggregate-only mixture. 

Mixture Data and Strength Test Results Specific data for the constituents, 
and the average strength data for each mixture are shown in Table 48 (page 
188) • The strength data shown were obtained from averages of three, 3x6-inch 
(7.6x15.2 cm), cylinders in most cases. Some averages were based on two spe- 
ciments when one specimen was damaged in handling. Compressive and tensile 
strength values were computed from P/A and 2P/77DL calculations respectively, 
where P was the total machine load, A was the cross sectional area, D was 
the diameter and L was the length of the 3x6- inch (7.6x15.2 cm) cylinders. 
Symbols used in the identification of the mixtures in Table 48 were as 
follows : 

Letters A, B and C refer to gradations 

Letter W refers to SSD aggregate 

Letter S refers to vacuum saturated aggregate 

Letter L refers to all synthetic aggregates 

Letter M refers to coarse synthetic and sand aggregate 

Letter E refers to extruded synthetic aggregate 

Numbers 5, 6, 7 and 8 refer to cement factors 

Other numbers refer to repeated mixtures 

Other letters refer to mixture series described for Table 45. 

The values for slump shown in Table 48 reflect the changes in consis- 
tencies of the concrete mixtures due to changes in test parameters such as 
aggregate gradation, aggregate moisture content, cement factor, etc., for 
constant water-cement ratios by weight. In general, anticipated changes 
occurred in the slump with changes in parameters, but some of the data 
appeared erratic. For example, increases occurred in the slumps of mixtures 
CWM-5, 6, 7 and 8 (all with w/c ratios = 0.68) when the water contents 
increased with higher cement factors. On the other hand, the slumps varied 
without explanation or reason in the preparation of mixtures CWM-5E. The 
large increase in the slump of AWM-6E4 over those for AWM-6E2 and 3 was 
attributed to an inadvertant pick-up of moisture by the aggregate during 
storage. 

54 



Large uncorrelated variations were observed in the air volume contents 
as shown in column (4) of Table 48. The air values were obtained by means 
of a laboratory type Protex Meter as described in AASHTO-152. It was recog- 
nized that the lightweight, high porosity character of the aggregate did not 
comply strictly with the provisions of the test procedure. The test run 
primarily for comparative information related to the performance of the dura- 
bility test specimens. Air contents also were measured by the Chace Indica- 
tor as a check on three (CSM-7, CWM-7B and BSM-7) mixtures with considerably 
lower values indicated. On the other hand, computations of air by the gravi- 
metric method for the same three mixtures produced values somewhat higher 
than those measured by the pressure method. From these observations, some 
doubt remains regarding the true air contents of the mixtures. 

Mixtures prepared with the cast aggregates were used to establish per- 
formance trends in the aggregate characteristics. Therefore, a greater number 
of parametric combinations was investigated with the cast aggregates than 
was investigated with mixtures prepared with the extruded aggregates. Because 
of the limited amount of extruded aggregate available, it was considered de- 
sirable to develop comparative data with extruded aggregate only for those 
mixtures which exhibited superior properties with the cast aggregates. In 
addition, one series of extruded aggregate mixtures (AWM-6E) was used to 
study the reproducibility of mixing procedures and to obtain statistical 
properties for a concrete mixture which was proportioned for general purpose 
concrete applications, i.e., 3/4- inch (1.91 cm) top size aggregate, six bags 
per cubic yard mixture, and a workable consistency. This statistical analy- 
sis was based on three identical mixtures (AWM-6E1, 2 and 3) mixed on differ- 
ent days. A slightly higher W/C ratio (0.71 vs 0.68) was required for AWM- 
6E1 to obtain the 6- inch (15.2 cm) slump. Mixture AWM-6E4 was not included 
in the analysis because of excessively high slump. The statistical data 
shown in Table 49 (page 189) were based on three test specimens for each data 
element. 

Analysis and Discussion of Strength Tests The data of Table 49 indicate 
considerable variability in the average strengths within mixtures and also 
between mixtures. In view of the controls and care exercised in the prepa- 
ration of the laboratory mixtures and test procedures, it may be expected 

55 



that strength variations in commercial mixtures will be larger than those 
shown in Table 49. 

The data of Table 48 have been presented as obtained from the labora- 
tory tests. Without qualification, there appears to be little correlation 
among test variables. In explanation of some of the variability, difficul- 
ties have been cited previously regarding the control of the aggregate free- 
moisture in storage. Also, in many cases, the adhesive characteristic of 
the plastic concrete produced a strong bond on the surfaces of the molds in 
spite of a generous coating of mineral oil. Consequently, some specimens 
were chipped or damaged to an unknown extent as they were removed from the 
molds. These two known conditions for some mixtures quite likely produced 
low strength values for those mixtures. Usually, honeycombed test specimens 
could be expected from mixtures with low slumps, and poor workability. 
Figure 47 (page 136) shows test specimens molded from mixtures with differ- 
ent slumps. Different slumps necessarily occurred when a constant w/c ratio 
was used with a range of cement factors and aggregate gradations. 

Insofar as the strength test specimens provided credible values, the 
following comparison may be drawn. 

1. Water-cement ratio relationship: In general, the strength develop- 
ment of the concrete complied with the conventional w/c relationship of 
increasing strength with decreasing w/c ratios. Comparisons of the strengths 
for mixture series AWM-8 and CWM-7 provide data in support of this relation. 
However, the contribution of the aggregate versus the contribution of the 
cement paste to the strength of the concrete was not clearly delineated in 
the different mixture series as was anticipated. There did appear to be a 
"ceiling strength" influence (though again, not well defined) by the inherent 
strength of the aggregate as is suggested by comparing the strengths of mix- 
tures CWM-5 and CWM-5E at w/c ratios of 0.68. In these mixtures, the cast 
aggregate mixture was twice as strong as the extruded aggregate mixtures. 
However, it is not known what the absolute "ceiling strength" of the cast 
aggregate may have been in the lower w/c ratio mixtures. Some of the mix- 
tures with high w/c ratios, such as CWL-7 (0.90) and BWM-7 (0.90) produced 
high 28-day compressive strengths. In these cases, it is believed that 



56 



improved workability and well consolidated test specimens contributed pri- 
marily to the strength values. 

2. Cement- factor versus strength: A series of mixtures (CWM) was 
prepared with a constant w/c ratio (0.68) to study the effect of the cement 
factor (CF) in bags per cubic yard of concrete) upon the strength of the 
concrete. The splitting tensile strength of these mixtures remained nearly 
constant (358, 351 and 325 p.s.i. (2,467, 2,418 and 2,239 kN/m )). The 
compressive strength variations are plotted in Figure 47 (page 136) along with 
the variations for slumps of the same mixtures. Because the water content of 
the mixtures increased with increasing cement contents, there were also in- 
creases in the slump measurements. From the data in Figure 48 (page 137), the 
strength values seem to be influenced more by the slump than by the change 

in paste content. However, inspection of comparable data from AWM and BWM 
mixtures do not show any correlation between strength, slump and cement 
factor. 

3. Effect of aggregate gradation: Figures 49 and 50 present the re- 
lationship between the compressive strength and the (cast) coarse aggregate 
gradation for mixtures with other parameters held constant. These data 
clearly indicate a trend of improved performance on both 7- and 28-day 
strengths for mixtures containing aggregate gradations A, B and C respec- 
tively. This trend remains evident even after allowing for the standard 
deviations in strengths as developed in Table 49. The limited test data 
for the extruded aggregate mixtures do not indicate a similar beneficial 
effect of aggregate gradation. In fact, these data suggest no performance 
difference in mixtures varying only in aggregate gradation. It is not 
clearly understood why the C gradation appears to be better for the cast 
aggregate, but it may be speculated that the smaller sized particles have 
fewer structural defects. Or perhaps the increased surface area of the 
finer material may have resulted in somewhat more absorption of the mixing 
water with an effective reduction in the w/c ratio. The latter hypothesis 
may be either be substantiated or refuted by comparative data from other 
mixtures . 

4. Effect of aggregate types: Similar mixtures containing cast and 
extruded aggregates were BWM-5, CWM- 5, CSM-5 with w/c = 0.68 and BWM- 7 

57 



with w/c = 0.51. Comparisons of these mixtures show that the cast aggre- 
gate strengths are more than fifty percent greater than the extruded aggre- 
gate for both 7- and 28-day compressive and the tensile strengths. 

5. Fly ash replacement for cement: Cast-aggregate mixtures BWM-7 
and BWM-7F with w/c = 0.51 were comparable mixtures with a 10 percent by 
weight replacement of the portland cement with fly ash C„o The 7-day com- 
pressive strengths were comparable, the 28-day compressive strength was 
higher and the tensile strength was lower for the fly ash mixtures. Another 
series of four modified mixtures were prepared with the 10 percent fly ash- 
cement replacement and the inclusion of one-half sand and one-half synthetic 
fine aggregate. These mixtures required a higher w/c ratio (0.70) to pro- 
vide a workable mixture due to the synthetic fine aggregate inclusion. When 
compared with the unmodified similar mixtures, the tensile strengths of the 
modified mixtures were lower and both the 7-day and 28-day compressive 
strengths varied but were generally lower. While inconclusive, this limited 
investigation did not find the fly ash replacement mixtures to be of inferior 
quality and suggests that a cost benefit may be derived by partial replace- 
ment of portland cement with less expensive fly ash. 

Freeze-Thaw Durability Test Results The durability of several of the con- 
crete mixtures was investigated by means of freeze-thaw cyclic tests. Two 
different test procedures were used. A screening test was used initially 
in which a total of 15 different beam specimens (3x4x16 inches (7.6x10.2x40.6 
cm)) were alternately frozen in air at -10°F (-23°C) and thawed in a satu- 
rated lime water bath at 70°F (21°C) . Each freezing and thawing cycle ex- 
ceeded six hours in duration. The slow cyclic rate was selected to simulate 
natural exposure conditions and to accommodate the laboratory work schedule. 
The extended temperature range (70°F (21°C)) was selected to impose high 
thermal stresses on the aggregate particles. Transverse resonant frequencies 
were measured periodically to determine the rate of deterioration of the 
specimen. The screening test continued for a maximum of 50 cycles of freez- 
ing and thawing or until the ratio of the periodic dynamic modulus to the 
initial dynamic modulus was reduced to 0.6 or below. Six of the specimens 
which passed the screening test were then subjected to a follow-up test in 
accordance with AASHTO T-161. The latter test was conducted in the 

58 



laboratory of the Virginia Highway and Transportation Research Council. 
Table 50 (page 190) shows the results of the freeze-thaw tests. Each test 
specimen was a single beam. All six beams deteriorated badly in less than 
54 cycles in the follow-up test. Figure 51 (page 140) shows typical surface 
cracking of a specimen after the screening test and Figure 52 (page 141) shows 
the condition of the beams after 53 cycles in the follow-up test or a total 
of 103 cycles. Figure 53 (page 142) shows a close-up photograph of a sec- 
tioned surface in the beam shown in Figure 52. 

Discussion of Durability Tests 

The screening test indicated better performance for the mixtures which 
contained SSD aggregates than those which contained vacuum saturated aggre- 
gates. The cast aggregate appeared to perform better than the extruded. 
There was no clear indication of a difference between specimens cured for 
7- and 28-days, nor did the screening test indicate significant differences 
in specimens with different cement factors or different aggregate gradations . 
Further testing may reveal a superior performance with C- aggregate specimens 
relative to B-aggregate specimens as suggested by the data (CWM-7 vs BWM-7 
specimens) but it is doubtful in view of the reverse indication offered by 
the follow-up test. There was an indication of better performance of the 
higher cement factor mixtures in the follow-up case. It was apparent from 
the durability tests that none of the mixtures were suitable for concrete 
installations subjected to cyclic freeze-thaw exposure conditions. 

Examination of the interior surfaces of the specimens after the dura- 
bility tests revealed varying amounts of white deposits around the peri- 
pheries of aggregate particles as shown in Figure 53. Other particles in 
the specimen were outlined with a thin, dark line. There did not appear to 
be any differences in the appearance of the fracture surfaces which could 
be correlated with any of the experimental variables. However, there was 
a definite correlation between the amount and location of the white deposits 
and the surface condition of the test specimen. In every case, the white 
deposits were located near surface cracks and for several beams which had 
no visible surface cracks, there was no visible evidence of white deposits 
inside. Apparently these deposits resulted from a leaching behavior of the 



59 



aggregate in the presence of high moisture concentration. The dark lines 
observed around particles in some specimens did not correlate with anything. 
Dark lines were seen around some particles which were located inside beams 
with no surface cracks and free from any white deposits. Usually, but not 
always, dark lines were found in specimens with extensive surface cracking. 
Apparently these deposits resulted from an interaction with the cement 
paste at the surface of the aggregate particle. Neither chemical nor petro- 
graphic analyses were performed to determine the nature or source of the 
deposited material. 

Bituminous Concrete Mixture 

A laboratory investigation was conducted with one gradation of the 
cast coarse aggregate to evaluate its performance in a typical wearing 
course of bituminous concrete. Mixture preparation and testing were con- 
ducted by the Bituminous Section of the Virginia Highway and Transportation 
Research Council. A complete copy of the investigators 1 report is appended 
herewith. The properties of the mixture with the highest Marshall stability 
were as follows: 

(a) Asphalt content, percent - 20 

(b) Density, pcf - 93.6 

(c) Total voids, percent - 7.7 

(d) Voids filled, percent - 79.2 

(e) Flow - 17 

(f) Stability - 2325 

(g) VMA, percent - 37.1 

In summary, it was determined that the aggregate performed satisfac- 
torily in the laboratory study, but an optimum asphalt content of over 20 
percent was considered unusually high compared with rock-aggregate mixtures. 

The following conclusions are based on the variety of laboratory tests 
conducted to evaluate the properties of synthetic aggregates composed of 
lime, fly ash and sulfate materials. 

1. The cast aggregate exhibited high absorption characteristics which 
resulted in difficult moisture control when used as a port land cement 



60 



concrete aggregate and in high asphalt demand when used as a bituminous 
concrete aggregate. 

2. The cast aggregate did not pass standard soundness tests for 
chemical stability nor for resistance to freezing and thawing. 

3. Neither cast nor extruded aggregates passed the Los Angeles Test 
for abrasion. 

4. The 28-day compressive strength of the moist-cured cast aggregate 

2 
(in 2-inch (5.1 cm) cubes) was approximately 1100 p.s.i. (7,579 kN/m ). 

It was necessary to post-cure the moist- cured extruded aggregate at 120°F 

(49°C) to achieve sufficient strength for use as a concrete aggregate. 

5. Approximately 1/3 of the original cured aggregate was wasted 
due to the production of fines during crushing and grading. 

The following conclusions are based on a variety of tests to evaluate 
the performance of synthetic aggregate in port land cement and bituminous 
concrete mixtures . 

1. Mixtures composed entirely of well graded coarse and fine syn- 
thetic aggregates were unworkable even at high water contents. Substitu- 
tion of a sand aggregate for the fine aggregate fraction provided workable 
mixtures. 

2. The water cement ratio law appeared to hold for the port land 
cement concrete mixtures . 

3. The effect of enriched pastes upon compressive strength was not 
apparent over a cement factor range of 5 to 8 bags per cubic yard. 

4. There was an increase in strength properties with a decreasing 

top size of coarse aggregate ranging from 3/4 to 3/8 inches (1.9 to 0.9 cm). 
The reasons for the increase in strength were not determined. 

5. The cast aggregate mixtures exhibited approximately 50 percent 

higher strength values than the extruded aggregate mixtures. Values for 

2 
cast aggregate mixtures were around 2500 p.s.i. (17,225 kN/m compared 

2 
with around 1500 p.s.i. (10,335 kN/m ) compressive strength for the extruded 

aggregate mixtures after 28 days of moist curing. 

6. Concrete mixtures may perform satisfactorily in warm climates 
not subject to freezing and thawing. None of the mixtures were considered 
suitable for prolonged exposure to freezing and thawing conditions. The 

61 



mixtures containing SSD aggregates exhibited better performance than those 
containing vacuum- saturated aggregates. 

7. Apparent leaching of the aggregates occurred during the freeze- 
thaw testing with the deposition of an unidentified white material at the 
surfaces of aggregate particles throughout the concrete specimens. The 
deposits were concentrated in regions of surface cracks. 

8. The aggregates exhibited satisfactory performance in Marshall test 
specimens of bituminous concrete. Approximately 20 weight percent of asphalt 
was required to achieve optimum properties. 



62 



SUMMARY OF RESULTS 

Based on the studies using pure gypsum, it has been found that calcium 
sulfate does enhance strength development of lime- fly ash-water mixtures. 
The optimum composition for maximum compressive strength was obtained with 
a lime to sulfate weight ratio of approximately 1:1. At this ratio, the 
28 day strength was about five times greater than if no gypsum was added. 
Besides composition, the other most important variables were the source of 
fly ash and the consistency of the sample, that is, whether it was compacted, 
extruded or of three inch slump consistency. Curing temperature was also 
found to be important, with strength development severely retarded by low 
temperature curing. Admixtures normally used to enhance pozzolanic reactions 
were found to have little effect on strength development as did lime replace- 
ment by portland cement. 

Studies of compound formation showed that morphological and mineralog- 
ical changes were evident as early as two days. Crystals representing re- 
action product were seen to form in the pore areas between fly ash spheres 
and by three months become the predominant morphological feature. Mineralog- 
ical examination indicated that a calcium sulfoaluminate hydrate was being 
formed . 

Waste sulfates were found to increase strength development when added 
to lime- fly ash-water mixtures, though generally not to the same extent as 
pure calcium sulfate. Engineering evaluation of selected formulations in- 
corporating waste sulfates showed: 1) the compacted dry density was lower 
than most compacted soils; 2) the California bearing ratio was quite high 
and exceeded that of the well graded crushed stone standard; 3) the perme- 
abilities were low, similar to that of a sandy or silty clay; and 4) dura- 
bility as measured by freeze-thaw and wet-dry tests was insufficient when 
samples were cured for 7 days at 73°F (23°C). 

Aggregate was prepared from mixtures of lime- fly ash-waste sulfate 

and water and evaluated for its properties and in portland cement and 

bituminous concrete. The aggregate itself when used after it had developed 

2 
a compressive strength of 1,100 p.s.i. (7,579 kN/m ) had high absorption 

63 



characteristics and did not pass standard soundness tests nor the Los 
Angeles abrasion test. When used in conjunction with port land cement, the 
concrete gave the highest compressive strength with the smallest (3/8 inch 
(0.9 cm)) top size coarse aggregate. Sand was necessary for the fine sized 
aggregate to improve workability. These Portland cement concrete mixtures 
may perform satisfactorily in warm climates not subjected to freezing and 
thawing. Also, the aggregates exhibited satisfactory performance in Marshall 
test specimens of bituminous concrete. However, approximately 20 weight 
percent of asphalt was required to achieve optimum properties. 



64 



RECOMMENDATIONS FOR FUTURE RESEARCH 

Mixtures of lime- fly ash-waste sulfate and water at a compact ible con- 
sistency have been found to have many adequate properties in laboratory 
experiments. It is recommended that field tests be performed using such 
a composition as a base course, sub-base or embankment being sure that ade- 
quate protection against freezing and thawing is afforded. 

It is also recommended that further laboratory research be conducted. 
Other waste sulfates should be tested for strength and durability proper- 
ties to gain information on the variability to be expected between waste 
types and waste sources. Correlation of these properties and others with 
morphological changes should be obtained. An evaluation of the freeze- thaw 
durability as a function of curing time should be undertaken to determine if 
increased curing time would improve this property. Also alternate methods 
of freeze-thaw evaluation should be studied to determine the most applicable 
method for this material. 

Continued study of aggregate prepared utilizing waste sulfate should 
also be extended. Strength and morphological evaluation have indicated 
that increased curing time, at least six to nine months, should produce 
a stronger and more resistant aggregate particle. This should then be 
evaluated for its soundness properties as well as in combination with port- 
land cement and a lime- fly ash-water or lime- fly ash-sulfate-water binder. 



65 



APPENDICES 



66 



APPENDIX A 
Data For Moisture-Density Relationship of Compactible Mixtures 

Moisture Content -a 
percent Dry Density, lb/ft 

Fort Martin Fly Ash 

16.6 88.6 

18.8 89.8 

20.9 90.0 
23.3 87.2 



Fort Martin Fly Ash 



18.8 87.8 

20.4 88.8 

21.7 87.9 

23.8 85.3 



Black Dog Fly Ash 



17.5 81.3 

18.3 82.7 

20.4 83.5 

23.8 83.9 

25.6 82.1 

29.9 77.8 



Amax Fly Ash 



Amax Fly Ash 



18.7 85.5 

20.3 86.9 

23.1 86.6 

24.0 86.5 

25.0 86.6 

26.7 85.2 

27.3 83.4 

d 



23.3 85.2 

23.9 87.1 

26.8 85.4 

28.1 84.0 



Albright Fly Ash 



16.4 88.2 

18.3 88.4 

20.2 89.1 

22.6 85.2 



67 



APPENDIX A (Continued) 

Moisture Content a 

percent Dry Density, lb/ft 



Hatfield's Ferry Fly Ash 



16.3 86.4 

18.4 86.6 
20.6 86.6 
23.4 85.0 
26.9 80.8 



a. 1 lb/ ft 3 =16.0 kg/m 3 

b. 80 percent fly ash, 12 percent lime, 8 percent gypsum 

c. 92 percent fly ash, 2.7 percent lime, 5.3 percent gypsum 

d. 92 percent fly ash, 3.2 percent lime, 4.8 percent gypsum 



68 



APPENDIX B 

Data for Analysis of Variance 
1. Compactible and slump mixtures after 7 days curing, 



***AN0VA 14:10 



12/26/73 



FACT0R 



LEVEL 



2 


2 LIMES 






3 


5 FLY ASH 






4 


2 WATER 






5 


3 SULFATES 






LINE 


VARIANCE * 


SUM 0F 


DEGREES 0F 


N0. 


C0MP0NENT 


SQUARES 


FREED0M 


1 
2 


_CMP{ 1 i -. 


1.6254E-4 
3.80334E-2 


2 
1 


CMP< 2 ) 


3 


jflpr 19 ^ - 


1.91535E-3 
4.46055 
8.1 2098 E-3 
.250521 


2 


4 
5 

6 


CMP( 3 ) 


4 
8 
4 


CMP( 23 ) 


7 


C«4"+g*-«* 


6.91275E-3 


8 


8 


CMP( 4 ) 


28.8729 


1 


9 
10 


PMPf 14 5j 


5.31 628 E-3 
•143186 


2 
1 


CMP( 24 ) 


11 


•GWW — 124 ) 


6.45303E-4 


2 


12 


C«P< 34 ) 


•288286 


4 


13 


PMDf UAA- 


1 .832 52 E- 2 


g 


14 


CMP( 234 ) 


A * WWW «*C* !■> fc* 

7.64599E-2 


w 

4 


15 




8.92976E-3 


8 




li 


CMP( 5 ) 


.491603 


2 


17 


*CMP( |g-» 


4.60608E-3 


4 


18 


CMP< 25 ) 


2.16397E-2 


2 


19 


XHPt ia»-) 


3.56266E-3 


4 


20 


CMP( 35 ) 


.157426 


8 


21 


PMPf 1 Hf^ ■>— - 


1. 39668 E-2 
.169712 


16 
8 


22 


CMP( 235 ) 


23 


'TMPf 125* > 


3.4284 7E-2 
8.17504E-3 
1.25661 E-2 
2.31821 E-2 


16 


24 
25 
26 


CMP( 45 ) 


2 

4 
2 


CMPC 245 ) 


27 
28 




2.02942E-3 
.133917 


4 
8 


CMP( 345 ) 


29 


GMW— Mr*5~>« 


2.23863E-2 


16 


30 


CMP( 2345 ) 


7.31 148 E-2 


8 


31 


CflEC- 1Q3-4S »* 


2.00042E-2 


16 


T0TAL 




35.3725 


179 



MEAN 

SQUARES 
- g . 1 26995 -5- 

3.80334E-2 
-a^W-7t-4 

1.11514 
J^OL54££-3 

6.26303E-2 

fl.fiifmF-l 

28.8729 
A , 6i Q 14E " 3 

.143186 

«^r&&65«-E-4« 

7.20715E-2 



.019115 
4>wt rvEZE "o 

.245801 
J-rA4+42€~3 
1.08199E-2 
&.90664S.J1 
1.96782E-2 
&^3 a&tiOE 4 - 
.021214 

4.08752E-3 
3 ^141DaC 3 " 



1.1 59 11 E-2 * 
■ r >,078fi g iE"^ 
1.67396E-2 * 

9.13935E-3 * 
1 ,?'ing6r«^ 



69 



APPENDIX B (Continued) 
Data for Analysis of Variance 
1. Compactible and slump mixtures after 7 days curing. (Continued) 



* E.G., CMP (12) MEANS C0MP0NENT 0F FACT0RS 1 AND 2 

GRAND MEAN 2.15919 

D0 Y0U WISH T0 P00L THE C0MP0NENTS7YES 

2010 DATA ITEM N0T VALID * qq , 

N0W AT 2010 + 

R£AD y CONF. LEVEL 

G0T0 2010 + ALM0ST « 95 

?1 CONF. LEVEL 

TYPE, WHEN REQUESTED, THE LINE NUMBERS 0F THE C0MP0NENTS 
IN P00L 1 (0NE LINE PER REQUEST). TYPE T0 SIGNAL THE LAST 
C0MP0NENT IN THE P00L HAS BEEN ENTERED. 
LINE, PLEASE71 
LINE, PLEASE73 
LINE, PLEASE75 
LINE, PLEASE77 
LINE, PLEASE79 
LINE, PLEASE711 
LINE, PLEASE713 
LINE, PLEASE715 
LINE, PLEASE717 
LINE, PLEASE719 
LINE, PLEASE721 
LINE, PLEASE723 
LINE, PLEASE725 
LINE, PLEASE727 
LINE, PLEASE729 
LINE, PLEASE731 
LINE, PLEASE70 
LINE N0. 
.J^ 32 P00L 1 .163734 120 1.36445E-3 

D0 Y0U WISH T0 CREATE M0RE P00LS N0W7O 
D0 Y0U WISH T0 C0MPUTE F-RATI0S7O 
D0 Y0U WISH T0 RETURN T0 THE P00LING PHASE70 

END 0F AN0VA 
N0W AT END 
READY 
0FF 



70 



APPENDIX B (Continued) 
Data for Analysis of Variance 
2. Compactible mixture after 7 days curing. 



***AN0VA 10:04 05/21/74 










FACT0R LEVEL 










1 3 REPLICATIONS 










2 2 LIME 










3 5 FLY- ASH 










4 3 SULFATE 










LINE VARIANCE * 


SUM 0F 


DEGREES 0F 


MEAN 




N0. C0MP0NENT 


SQUARES 


FREED0M 


SQUARES 




1 CMPC 1 ) 


2.8761 1E-3 


2 


^^p^^TJTT^ U vj l_*"*0 




2 CMPC 2 ) 


1.68136E-2 


1 


1.68136E-2 


* 


3 CMPC 12 ) 


2.04619E-3 


2 


1.02309E 3 




4 CMPC 3 ) 


2.46333 


4 


.615832 


* 


5 CMPC 13 ) 


1.63192E-2 


8 


■3~ t 0»9PE-3 




6 CMPC 23 ) 


.16598 


4 


.041495 


* 


7 CMPC 123 ) 


5- 13478E-3 


a 


c AIRrtflF-4 




8 CMPC 4 ) 

9 CMPC 14 ) 

10 CMPC 24 ) 


.186495 

3.78102E-3 

3.02833E-2 


o 

2 

4 
2 


9.32473E-2 


* 


1.51417E-2 


* 


11 CMPC 124 ) 


4.3501 1E-3 


4 


„1.0g7MF"ft- 




12 CMPC 34 ) 


8.64458E-3 


8 


1.08057E-3 


NO 


13 CMPC 134 ) 

14 CMPC 234 ) 


1.68988E-2 
4.99512E-2 


16 

8 






6.2439E-3 


* 


15 CMPC 1234 ) 
T0TAL 


2.98277E-2 
3.00273 


16 

89 










* E.G., CMPC 12) MEANS C0MP0NENT 0F FACT0RS 


1 AND 2 


* .95 + 




GRAND MEAN 2.5597 






CONFIDENCE LEVEL 


D0 Y0U WISH T0 P00L THE C0MP0NENTS71 








TYPE, WHEN REQUESTED, THE LINE 


NUMBERS 0F 


THE C0MP0NENTS 






IN P00L 1 C0NE LINE PER REQUEST). TYPE 


T0 SIGNAL THE 


LAST 




C0MP0NENT IN THE P00L HAS BEEN 


ENTERED. 








LHE, PLEASE71 










LINE, PLEASE73 










LINE, PLEASE75 










LINE, PLEASE77 










LINE, PLEASE79 










LINE, PLEASE711 










LINE, PLEASE? 13 










LINE, PLEASE715 










LINE, PLEASE70 











71 



APPENDIX B (Continued) 
Data for Analysis of Variance 
2. Compactible mixture after 7 days curing. (Continued) 



LINE N0. 

16 
D0 Y0U WI 
D0 Y0U VI 
TYPE THE 
EFFECT an 
LINE F0R 
LINE F0R 
F-RATI0 = 
D0 Y0U WI 
LINE F0R 
LINE F0R 
F-RATI0 = 
D0 Y0U WI 
LINE F0R 
LINE F0R 
F-RATI0 = 
D0 Y0U WI 
LINE F0R 
LINE F0R 
F-RATI0 = 
D0 Y0U WI 
LINE F0R 
LINE F0R 
F-RATI0 r 
D0 Y0U WI 
LINE F0R 
LINE F0R 
F-RATI0 = 
D0 Y0U WI 
LINE F0R 
LINE F0R 
F-RATI0 = 
D0 Y0U WI 
D0 Y0U WI 



P00L 1 .081234 60 

SH T0 CREATE M0RE P00LS N0W7O 
SH T0 C0MPUTE F-RATI0S71 
LINE NUMBER. WHEN REQUESTED. F0R 



1.3539E-3 



ERROR 



(A) THE MAIN 



F0R THE ERR0R TERM. 



I , 60) 
F-RATI0S N0W?1 



60 ) 



INTERACTI0N, AND (B) 
(A), PLEASE72 
(B), PLEASE716 

12.4186 (D.F. = 
SH T0 C0MPUTE M0RE 
(A), PLEASE74 
(B), PLEASE716 

454.858 (D.F. = 
SH T0 C0MPUTE M0RE F-RATI0S N0W71 
(A), PLEASE76 
(B), PLEASE716 

30.6485 (D.F. r 4 , 60 ) 
SH T0 C0MPUTE M0RE F-RATI0S N0W71 
(A), PLEASE78 
(B>, PLEASE716 

68.8731 (D.F. = 2 , 60 ) 
SH T0 C0MPUTE M0RE F-RATI0S N0W71 
(A), PLEASE710 
(B), PLEASE716 

11.1837 (D.F. = 
SH T0 C0MPUTE M0RE 
(A) , PLEASE712 
(B) f PLEASE716 

798 118 ( D F r 
SH # T0 C0MPUTE*M0RE F-RATI0S N0W71 
(A), PLEASE714 
<B), PLEASE716 

4.61179 (D.F. = 
SH T0 C0MPUTE M0RE 
SH T0 RETURN T0 THE 



2 , 60 ) 
F-RATI0S N0W71 



60 ) 



* * * 



* * * 



* * * 



•k -k it 



•k it it 



NO 



8 , 60 ) 
F-RATI0S N0W7O 
P00LIN6 PHASE70 



* * * 



END 0F AN0VA 

N0W AT END 

SRU'S:2.2 

READY 

0FF 



72 



APPENDIX B (Continued) 

Data for Analysis of Variance 
3. Compactible and slump mixtures after 28 days curing. 
RUN 

***AN0VA 13:51 05/21/74 
FACT0R LEVEL 



1 

2 




3 
2 








3 




5 








4 




2 








5 




3 








LINE 


VARIANCE * 


SUM 0F 


DEGREES 0F 


MEAN 


N0. 


C0MP0NENT 


SQUARES 


FREED0M 


SQUARES 


1 


CMPC 


1 ) 


6.12848E-3 


2 


■ 3»0Me*E«-3~— 


2 


CMPC 


2 ) 


.341783 


1 


.341783 * 


3 


CMPC 


12 ) 


1.12393E-2 


2 


_5-64-9«-eFvr 


4 


CMPC 


3 ) 


4.34347 


4 


1 .08587 * 


5 


CMPC 
CMPC 


13 ) 


1.1 5961 E-2 
3.44526E-2 


8 
4 




6 


23 ) 


8.61314E-3 •* 


7 


CMPC 


123 ) 


2.051 31 E-2 


8 


-Z+S&tt+E'f-" 


8 


CMPC 


4 ) 


7.82925 


1 


7.82925 * 


9 


CMPC 


14 ) 


4.85376E-5 


2 


Z< irrifftrr v 


10 


CMPC 


24 ) 


.198686 


1 


.198686 * 


11 


CMPC 


124 ) 


3.15626E-3 


2 


i»fl7cnar""fl 


12 


CMPC 


34 ) 


.803106 


4 


.200776 


13 


CMPC 


134 ) 


9.54197E-3 


8 


XUA2a^E-3— 


14 


CMPC 


234 ) 


.090596 


4 


.022649 ' * 


15 
16 


CMPC 
CMPC 


1234 ) 
5 ) 


2.70971 E-2 
.264286 


8 
2 




.132143 * 


17 


CMPC 


15 ) 


1.19894E-2 


4 


2_aso3&£«& 


18 
19 
20 


CMPC 
CMPC 
CMPC 


25 ) 
125 ) 
35 ) 


.120814 

6.09333E-3 

.407479 


2 

4 

8 


6.04072E-2 * 


5.09349E-2 * 


21 


CMPC 


135 ) 


3.65211E-2 


16 


g,agpwg-a* 


22 


CMPC 


235 ) 


.236636 


8 


2.95795E-2 * 


23 
24 


CMPC 
CMPC 


1235 ) 
45 ) 


3.13662E-2 
.242913 


16 
2 




.121457 * 


25 
26 


CMPC 
CMPC 


145 ) 
245 ) 


1.41625E-2 
6.63074E-3 


4 
2 




3.31537E-3 NC 


27 
28 


CMPC 
CMPC 


1245 ) 
345 ) 


5.85432E-3 
.237 


4 

8 




.029625 * 


29 


CMPC 


1345 ) 


3.89943E-2 


16 


.2.4871 IF > 


30 


CMPC 


2345 ) 


.254079 


8 


3.17599E-2 * 


31 


CMPC 


12345 ) 


3.30832E-2 
15.6786 


16 
179 




T0TAL 





73 



APPENDIX B (Continued) 
Data for Analysis of Variance 
3. Compactible and slump mixtures after 28 days curing. (Continued) 

* E.G., CMPC12) MEANS C0MP0NENT 0F FACT0RS 1 AND 2 * 95 + 

GRAND MEAN 3.0758 CONFIDENCE 

D0 Y0U WISH T0 P00L THE C0MP0NENTS71 mvEh 

TYPE, WHEN REQUESTED, THE LINE NUMBERS 0F THE C0MP0NENTS 

IN P00L 1 (0NE LINE PER REQUEST). TYPE T0 SIGNAL THE LAST 

C0MP0NENT IN THE P00L HAS BEEN ENTERED. 

LINE, PLEASE?! 

LINE, PLEASE73 

LINE, PLEASE75 

LINE, PLEASE?? 

LINE, PLEASE79 

LINE, PLEASE?! 1 

LINE, PLEASE? 13 

LINE, PLEASE715 

LINE, PLEASE? 17 

LINE, PLEASE? 19 

LINE, PLEASE721 

LINE, PLEASE723 

LINE, PLEASE725 

LINE, PLEASE727 

LINE, PLEASE729 

LINE, PLEASE731 

LINE, PLEASE70 

LINE N0. 

32 P00L 1 .267385 120 2.22821 E-3 ERROR 
D0 Y0U WISH T0 CREATE M0RE P00LS N0W7O 
D0 Y0U WISH T0 C0MPUTE F-RATI0S71 

TYPE THE LINE NUMBER, WHEN REQUESTED, F0R (A) THE MAIN 
EFFECT 0R INTERACTI0N, AND (B) F0R THE ERR0R TERM. 
LINE F0R (A), PLEASE72 

LINE F0R (B), PLEASE732 * 

F-RATI0 = 153.389 (D.F. = 1 , 120 ) 
D0 Y0U WISH T0 C0MPUTE M0RE F-RATI0S N0W71 
LINE F0R (A), PLEASE74 
LINE F0R (B), PLEASE732 

F-RATI0 r 487.327 (D.F. = 4 , 120 ) * 
D0 Y0U WISH T0 C0MPUTE M0RE F-RATI0S N0W71 
LINE F0R (A), PLEASE76 
LINE F0R (B), PLEASE732 

F-RATI0 : 3.8655 (D.F. = 4 , 120 ) * 
D0 Y0U WISH T0 C0MPUTE M0RE F-RATI0S N0W71 
LINE F0R (A), PLEASE78 
LINE F0R (B), PLEASE732 

F-RATI0 r 3513.7 (D.F. = 1 , 120 ) * 
D0 Y0U WISH T0 C0MPUTE M0RE F-RATI0S N0W71 



74 



APPENDIX B (Continued) 
Data for Analysis of Variance 
3. Compactible and slump mixtures after 28 days curing. (Concluded) 



LINE F0R (A), PLEASE710 






LINE F0R (B), PLEASE732 






F-RATI0 = 89.1682 (D.F. = 


1 , 120 


) 


D0 Y0U WISH T0 C0MPUTE M0RE 


F-RATI0S 


N0W71 


LINE F0R (A), PLEASE?! 2 






LINE F0R (B), PLEASE732 






F-RATI0 r 90.1066 (D.F. = 


4 , 120 


) 


D0 Y0U WISH T0 C0MPUTE M0RE 


F-RATI0S 


N0W71 


LINE F0R (A), PLEASE714 






LINE F0R (B), PLEASE732 






F-RATI0 = 10.1647 (D.F. = 


4 , 120 


) 


D0 Y0U WISH T0 C0MPUTE M0RE 


F-RATI0S 


N0W71 


LINE F0R (A), PLEASE716 






LINE F0R (B), PLEASE732 






F-RATI0 = 59.3045 (D.F. = 


2 , 120 


) 


D0 Y0U WISH T0 C0MPUTE M0RE 


F-RATI0S 


N0W71 


LINE F0R (A), PLEASE? 18 






LINE F0R (B), PLEASE732 






F-RATI0 r 27.1102 (D.F. = 


2 , 120 


) 


D0 Y0U WISH T0 C0MPUTE M0RE 


F-RATI0S 


N0W71 


LINE F0R (A), PLEASE720 






LINE F0R (B), PLEASE732 






F-RATI0 = 22.8591 (D.F. = 


8 , 120 


) 


D0 Y0U WISH T0 C0MPUTE M0RE 


F-RATI0S 


N0W71 


LINE F0R (A), PLEASE722 






LINE F0R (B), PLEASE732 






F-RATI0 r 13.275 (D.F. = 


8 , 120 3 




D0 Y0U WISH T0 C0MPUTE M0RE 


F-RATI0S 


N0W71 


LINE F0R (A), PLEASr?24 






LINE F0R (B), PLEASE732 






F-RATI0 r 54.5086 (D.F. r 


2 , 120 


) 


D0 Y0U WISH T0 C0MPUTE M0RE 


F-RATI0S 


N0W71 


LINE F0R (A), PLEASE726 






LINE F0R (B), PLEASE732 






F-RATI0 = 1.48791 (D.F. = 


2 , 120 


) 


D0 Y0U WISH T0 C0MPUTE M0RE 


F-RATI0S 


N0W71 


LINE F0R (A), PLEASE728 






LINE F0R (B>, PLEASE732 






F-RATI0 = 13.2954 (D.F. = 


8 , 120 


) 


D0 Y0U WISH T0 C0MPUTE M0RE 


F-RATI0S 


N0W71 


LINE F0R (A), PLEASE730 






LINE F0R (B), PLEASE732 






F-RATI0 = 14.2535 (D.F. = 


8 , 120 


) 


D0 Y0U WISH T0 C0MPUTE M0RE 


F-RATI0S 


N0W7O 


D0 Y0U WISH T0 RETURN T0 THE 


! P00LING 


PHASE70 



NO 



75 



APPENDIX B (Continued) 
Data for Analysis of Variance 
4. Compactible mixture after 28 days curing. 



ACT0R 



LEVEL 



1 


3 


REPLICATIONS 




2 


2 


LIMES 








3 


5 


FLY- ASH 






4 


3 


SULFATE 






LINE 


VARIANCE * 






SUM 0F 


DEGREES 0F 


N0. 


C0MP0NENT 






SQUARES 


FREED0M 


1 


CMPC 1 ) 






2.6838 1E-3 


2 


2 


CMP( 2 ) 






9.64392E-3 


1 


3 


CMPC 12 ) 






1.12686E-2 


2 


4 


CMPC 3 ) 






1.01914 


4 


5 


CMPC 13 ) 






1.07949E-2 


8 


6 


CMPC 23 ) 






5.41061E-2 


4 


7 


CMPC 123 ) 






3.73555E-2 


8 


8 


CMPC 4 ) 






1.26253E-3 


2 


9 


CMPC 14 ) 






4.19833E-3 


4 


10 


CMPC 24 ) 






4.06566E-2 


2 


11 


CMPC 124 ) 






6.8664E-3 


4 


12 


CMPC 34 ) 






4.27363E-2 


8 


13 


CMPC 134 ) 






3.99997E-2 


16 


14 


CMPC 234 ) 






5.92873E-2 


8 


15 


CMPC 1234 ) 






2.63169E-2 


16 


T0TAL 








1.36632 


89 


* E.G. 


,, CMPC 12) MEANS 


! C0MP0NENT 0F FACT0RS 


1 AND 2 


GRAND 


MEAN 3,28435 








D0 Y0U WISH T0 P00L THE C0MP0NENTS?! 




TYPE, 


WHEN REQUESTED. 


THE 


LINE 


NUMBERS 0F 


THE C0MP0NENTS 


IN P00L 1 (0NE LINE 


: PER 


REQUEST). TYPE 


T0 SIGNAL THE 


C0MP0NENT IN THE P00L 


. HAS 


BEEN 


ENTERED. 




LINE, 


PLEASE? 1 










LINE, 


PLEASE73 










LINE, 


PLEASE75 










LINE, 


PLEASE77 










LINE, 


PLEASE79 










LINE, 


PLEASE?! 1 










LINE, 


PLEASE713 










LINE, 


PLEASE715 










LINE, 


PLEASE70 











MEAN 
SQUARES 
1, 8 4191 - 3 i 
9.64392E-3 * 

.254786 * 

-i,<H93TE J" 
l,35265E-2 * 
fl.ffff*rtir-» 
6.31263E-4 NO 
i.nrtfl5ffK-ft 
2.03283E-2 * 
U . 71CCE g * 
5.34204E-3 /NO 
2.10P90E fl 
7.41091E-3 * 

t f k Ufa i 

* .95 + 
' CONFIDENCE 
LEVEL 



LAST 



APPENDIX B (Concluded) 
Data for Analysis of Variance 
4. Compactible mixture after 28 days curing. (Continued) 



LINE N0. 

16 
D0 Y0U WI 
D0 Y0U WI 
TYPE THE 
EFFECT 0R 
LINE F0R 
LINE F0R 
F-RATI0 = 
D0 Y0U WI 
LINE F0R 
LINE F0R 
F-RATI0 = 
D0 Y0U WI 
LINE F0R 
LINE F0R 
F-RATI0 : 

D0 Y0U WI 
D0 Y0U WI 
LINE F0R 
LINE F0R 
F-RATI0 = 
D0 Y0U WI 
LINE F0R 
LINE F0R 
F-RATI0 r 
D0 Y0U WI 
LINE F0R 
LINE F0R 
F-RATI0 = 
D0 Y0U WI 
LINE F0R 
LINE F0R 
F-RATI0 = 
D0 Y0U WI 
D0 Y0U WI 
D0 Y0U WI 
D0 Y0U WI 
D0 Y0U WI 



60 



P00L 1 ,139484 
SH T0 CREATE M0RE P00LS N0W7O 
SH T0 C0MPUTE F-RATI0S71 
LINE NUMBER, WHEN REQUESTED, F0R 

INTERACTI0N, AND (B) F0R THE 
(A), PLEASE72 
(B), PLEASE716 

4.1484 (D.F. = 
SH T0 C0MPUTE M0RE 
(A) f PLEASE74 
(B), PLEASE716 

109.598 (D.F. r 
SH T0 C0MPUTE M0RE F-RATI0S N0W71 
(A), PLEASE76 
(B), PLEASE716 

5.81852 (D.F. = 

SH T0 C0MPUTE M0RE 
SH T0 C0MPUTE M0RE 
(A), PLEASE78 
(B), PLEASE716 

.271542 (D.F. r 
SH T0 C0MPUTE M0RE 
(A), PLEASE710 
(B), PLEASE716 

8.74435 (D.F. = 
SH T0 C0MPUTE M0RE F-RATI0S N0W71 
(A), PLEASE712 
(B), PLEASE716 

2.29791 (D.F. = 8 , 60 ) 
SH T0 C0MPUTE M0RE F-RATI0S N0W71 
(A) , PLEASE714 
(B), PLEASE716 

3.18785 (D.F. r 8 , 60 ) 
SH T0 C0MPUTE M0RE F-RATI0S 

RETURN T0 THE P00LING 

P00L THE C0MP0NENTS7O 

C0MPUTE F-RATI8S70 

RETURN T0 THE P00LING PHASE70 



2.32473E-3 



ERROR 



(A) THE MAIN 
ERR0R TERM. 



1 , 60 ) 
F-RATI0S N0W71 



60 ) 



4 , 60 ) 

F-RATI0S N0W78 
F-RATI0S N0W71 



2 ,60) 
F-RATI0S N0W71 



60 ) 



JUST 



NO 



NO 



SH 
SH 
SH 
SH 



T0 
T0 
T0 
T0 



N0W7O 
PHASE71 



END 0F AN0VA 

N0W AT END 

SRU'Stl.4 

READY 

0FF 



77 



APPENDIX C 

Comparison of Properties of Synthetic 
Aggregates from Two Sources 



Minnick* 



U. Va. 



Unit Weight 

Grading Using, ASTM Size Number 

Soundness, Sodium Sulfate 

Weight Loss in 5 Cycles 

Los Angeles Abrasion 

Weight Loss (C Grading) 
(D Grading) 

Absorption 

15 Min. 
24 Hr. 

Strength Development 
7 Days at 73°F 
14 Days 
28 Days 

2 Months 

Compressive Strength of Concrete 
7 Days 
28 Days 

3 Months 



65 pcf 
7 

0.5% 

32.0% 



56 

67, 7 & 8 

27.8% 

44 and 70% 



7.9% 


Not determined 


9 . 1% 


18.5% 


181 psi 


150 psi 


533 psi 


470 psi 


1163 psi 


1170 psi 


1983 psi 


Not determined 


3340 psi 


2547 psi 


4041 psi 


3223 psi 


4379 psi 


Not determined 



*From "Structural Compositions Prepared From Inorganic Waste Products," 
Table 1, by L. John Minnick. Paper presented at the Annual Meeting of 
AASHO, Miami Beach, Florida, December 5-10, 1971. 



78 



APPENDIX D 
Report on the Los Angeles Abrasion Test 



79 



rotiM PR-221 (WO) 

nil v lo nni 



U.5. DLPAflTMHNT OF COMMI llf.l. 

nunr:Au or i*uni_ic iioahi 



REPORT ON SAMPLE OF SY N Tl± £flC A6G££&Am P KePAKCD- fR°* U*ti* 
/Z/ //5/^ 3ULrAT£ tM\ST£ MiXWlt£ 



LAOORATOHY NUMUEH 



IDENTIFICATION MARKS 

See be/ou/ 

DATE SAMPLEO 



TfUANTITV UPPHPftPHTFO 



; OATI. I" MOHTtl) 

4-/7-7J? 



SUOMITTI \i flY 



"ATE RECEIVED 

4-7-7S 



DATE RECEIVED 

4-7-7S 

-fiTJWR^t HF MA + t-BlAb 



SAMPLED FROM 



LOCATION USED OR TO BE USED 



EXAMINED FOR 



Abfcjs/oWj £o$ Angeles Machine^ 6-m^thjJD 



TEST RESULTS 



Laboratory /\Jo. 


/Vo/oe 


A/-6/7S 


/7-a/?& 


JjQeri tifi'c a t/cV ? 




Casf /Z7^/Vef 


&ct 8.<l5#A/et 






Pass*4 Ret #8 


ftss #4 &/ *S 






7-az-jr 


7-30-7^ 


• 


Specrfica,iic\n 








^qa'trcYnent'-i 






7o cf reyi/iWti Gawpk 


JD 


Modified J) 


Modified :d 


loo.o 


83.3 


(& fc>. / 


Mo. of spheres 


<0 


5 


4 


HasS of charge j o^ 


SLKOO±I5 


%0B5^rl 


/665+7/z 


KluSS c\ ~ti>iT sample^ cy 


50O0 ± 10 


4 16 &££ 


333S-±7 


Nb. of druto revolutions 


50O 


4l£ 


334- 


Test" Scimpie; 








OrgiVki/ b/eighlja/ 


.. 


A-IC6 


3335' 


Final We^htj a. 





Z3\£ 


996 


Lo59 /r 


— — 


I S/j'O 


339 


r»rce^T W-ear 




44 



70 



Mote 



Due To insuff/c/eht material, tV» e abrasion testas requested could r\ot betroc/e, 
XhsTead ex. fhodif^j 3 rcul iV>o. J) test" lA/as pev T orvY>ed cm each material 
Submitted. The t^odi-TVed i«?sT cons/s"fei c>f fredveinct proporTiovhxlly ihe sample 
weight, the movwber of spheres artd -fhe drg<n v.- volutins-. Xf fe K>ot Know* 
if these tests have any CcUrtrelatibn a/Z.k a. t<- if m<ide ontVie Same rticvtew) 
«ji<J ir?«<?tiK>g &|>ecf4f esccft'en requirements regqv^iVig savnpJe sfze. 



CHIEF, DIVISION OF PHYSICAL RFT.CAHCH 



OHM MA V 



■w 



PER 



0.H, Payer <?//& 



USCOMM DC 484»I-P«0 



APPENDIX E 
Report on Bituminous Mix Design for Synthetic Aggregates 



81 



REPORT ON 
BITUMINOUS MIX DESIGN FOR SYNTHETIC AGGREGATES 

by 

C. S. Hughes and G. W. Maupin, Jr., P.E.'s 
November 14, 1974 



82 



REPORT ON 
BITUMINOUS MIX DESIGN FOR SYNTHETIC AGGREGATES 

by 
C. S. Hughes andG. W. Maupin, Jr., P.E.'s 

INTRODUCTION 

The work reported herein is a determination of the optimum asphalt content for a 
surface mix grading of a synthetic aggregate supplied by Professor Fred McCormick. In 
addition to the Marshall Design results, the Virginia Department of Highways and Trans- 
portation stripping test results are also reported. 

OPTIMUM ASPHALT CONTENT 

Table I and Figure 1 summarize the results of the Marshall Design procedures. It 
should be noted that the volumetric data in Table I, i. e. , VTM, VFA, and VMA are based 
on a supplied aggregate specific gravity of 1. 9. As Table I shows, the trends of the above 
mentioned volumetric data as well as the unit weight follow the normal relationship between 
each of these properties and asphalt content. However, Figure 1 depicts the erratic pattern 
of stability and flow, primarily due to the results at the asphalt content of 21%. 

The variability of the results is further demonstrated in Table I where a comparison 
is made between results at 21% asphalt. The last row in this table is designated as an 
asphalt content of 21-R. This designation is used to indicate the mix was quite rich. The 
reason for the two greatly different results of the same asphalt content is absorption of the 
aggregate which Dr. McCormick reported as 20%. For all of the mixes except the 21-R, 
the aggregate was allowed to stand for 30 to 45 minutes between mixing and compacting. 
And thus, each mix used in the normal Marshall Design procedure, i.e. asphalt contents 
19 through 22, was allowed to absorb the same amount of asphalt by holding the time between 
mixing and compacting constant. However, for the 21-R mix, compaction was accomplished 
immediately after mixing. The excessive asphalt in this mix was that which would have been 
absorbed if more time had been allowed between mixing and compacting. 

As a practical use of this aggregate in a bituminous mix, the mixing, hauling, and 
placing times will have to be considered in the mix design. Otherwise the mix could be too 
dry or too rich for proper compaction and durability. 

83 



Form: R-91 
(Rev. 8-74) 



-2- 

TABLE I 
Virginia Highway & Transportation Research Council 



Bituminous Laboratory 
SUMMARY OF RESULTS-BITUMINOUS MIXES 
Project M^ Design for Synthetic Aggregate Date November 5, 1974 



Tests b y p.. S. Hughes fc fl. W. Maupin. Jr. Computations By_ 



Sample 
No. 


Asphalt 

% 


Density 
pcf 


Voids Total 

Mix 

% 


Voids Filled 
with Asphalt 

% 


Flow 


Stability 


Voids in 
Mineral Agg. 

% 




19 


90.9 


11.1 


71.0 


21 


785 


38.2 




20 


93.6 


7.7 


79.2 


17 


2325 


37.1 




21 


94.1 


6.5 


82.7 


. 28 


1085 


37.5 




22 


92.5 


7.4 


81.2 


17 


1720 


39.4 




















21 -R 


88.3 


12.3 


70.3 


32 


545 


41.4 











































































































































































84 

























































-3- 



Form n-153 (Rev. 10-16-62) 



94 



\ 93 



| 9Z 



z 
=» 91 



90 



Figure 1 
Marshall Design Charts 

Synthetic Aggregates 

VIRGINIA COUNCIL OP HIOHWAV 
INVESTIGATION AND RMfAftCH 



19 Zo 21 ZZ 

ASPHALT CONTENT, PERCENT 



256o 




























« 


( 












22OO0 








/ 


\ 


















/ 


\ 












|/5oo 

< 








' 




\ 




/ 


> 








/ 






\ 




V 






«/» 






/ 






\ 


/ 












< 


( 
















.^AA 























19 Zo zi zz 

ASPHALT CONTENT, PERCENT 



* ZS 
O 



2.0 



/^ 






/? 2,0 2/ 2.2 

ASPHALT CONTENT, PERCENT 















































/2. 










































IO 










































a 










































c 























/9 Zo 2,/ ZZ 

ASPHALT CONTENT, PERCENT 



65 



§ 60 

o 
hi 

u. 
in 
O 

O 70 



_ . 



19 ZQ ZI 2.2/ 

ASPHALT CONTENT, PERCENT 



85 



-4- 

The determination of the optimum asphalt content (Asphalt Institute Manual 
Series No. 2) and the corresponding mix properties are shown in Table II. 



TABLE II 

OPTIMUM ASPHALT CONTENT DETERMINATION 

Property Asphalt Content % 

Max. Unit Weight, pcf. 94.1 21 

Min. VTM, % 6.5 21 

Max. Stability 2325 20 

Optimum asphalt content, ave. 20. 7 



A value of 20. 7% asphalt is unusually high, but does reflect the high absorptive 
properties of the aggregate. Slightly more asphalt may be needed if the aggregate tends 
to dry out due to longer absorption times. 

Other than the unusual absorptive nature of this aggregate, there appears to be no 
reason why a satisfactory bituminous mix cannot be designed using it. The stabilities 
and volumetric properties are acceptable. Of course, the durability properties are 
unknown. 



STRIPPING TEST 

A modified form of the Virginia Test Method for Heat Stable Additive (Designation 
VTM-13) was used to determine the susceptibility of the coated aggregate to stripping. Due 
to the high absorption of the aggregate, 21 percent asphalt content was used rather than 
9.5 percent specified by VTM-13. 

The following procedure was followed: 

1. 1185 grams of aggregate was heated to 300°F and mixed with 315 grams of asphalt 
cement heated to 275°F. 

2. 300 grams of the hot mixture was placed in boiling water and boiling was continued 
for 10 minutes. 

3. The water was drained from the mixture and it was placed on a paper towel. 

4. After 12 hours the mixture was examined for signs of stripping. 

86 



-5- 

The results were negative indicating that stripping did not take place. 
There were some small particles that had uncoated surfaces, however, the 
uncoated surfaces were believed to be the result of broken particles. 



87 



REFERENCES 

1. Wilmoth, R C. and Hill, R. D., "Neutralization of High Ferric Iron 
Acid Mine Drainage," Program 14010 ETV, Federal Water Quality Admin- 
istration (1970). 

2. Aerospace Corporation, "Technical and Economic Factors Associated with 
Fly Ash Utilization," Contract No. F04701-70-C-0059, Environmental 
Protection Agency (1971). 

3. Jones, J. W. and Stern, R. D., "Waste Products from Throwaway Flue 
Gas Cleaning Processes-Ecologically Sound Treatment and Disposal," 

U. S. EPA Flue Gas Desulfurization Symposium, New Orleans, La. (1973). 

4. Minnick, L. J., "The New Fly Ash," Bureau of Mines Information Circular 
No. 8488, 269-281 (1970). 

5. Minnick, L. J., "Sulfopozzolanically Active Fly Ash and Composition," 
U. S. Patent 3,634,115 (1972). 

6. Coal Research Bureau, "Pilot Scale Up of Processes to Demonstrate 
Utilization of Pulverized Coal Fly Ash Modified by the Addition of 
Limestone-Dolomite Sulfur Dioxide Removal Additive," Contract CPA 
70-66, Environmental Protection Agency (1972). 

7. Cockrell, C. F., Muter, R. B. and Leonard, J. W., "Study of the Poten- 
tial for Profitable Utilization of Pulverized Coal Fly Ash Modified by 
the Addition of Limestone-Dolomite Sulfur Dioxide Removal Additives," 
Contract No. PH 86-67-122, National Air Pollution Control Administra- 
tion (1969). 

8. Minnick, L. J., "Structural Compositions Prepared from Inorganic Waste 
—Products," Annual Meeting of AASHO, Miami Beach, Florida (1971). 

9. Minnick, L. J., Webster, W. C. and Hilton, R. G., "Technical Control 
of Sulfate Waste Materials at Transpo '72 Site." NTIS Accession No. 
PB 228 975 (1973). 

10. Anday, M. C, "Curing of Lime-Stabilized Soils," Highway Research Board 
Record No. 29, 13-26 (1963). 

11. Winer, B. J., "Statistical Principles in Experimental Design," 2nd 
Edition, McGraw-Hill Book Co., New York, N. Y. (1971) p. 400. 



88 



6 r- 



LU 

IE 

o 



4 - 



o 
o 

UJ 

in 



o 



U~> 



3 - 



2 - 



1 ~ 



1 2 3 

SLUMP OF SMALL CONE, INCHES 
Figure 1. Calibration curve for slump cone. 



89 




Figure 2. Mixture at extrudable consistency. 



90 




Figure 3. Apparatus for measuring dimensional changes 



91 




C\J 



CO 
CM 



C\J 
C\J 



CO 



o 

CVJ 



C_3 

cm 

LU 



o 

C_> 



CO 

I— I 

o 



01 



00 



J3 
co 
cfl 

T-l 

c 

•H 
■U 

ctj 

a 

4J 
5-1 
O 

Fn 

00 

a 
•1-1 

CO 

c 

4-1 

a 

o 
o 

cu 

M 

4-) 
CO 

•r-< 
O 

S 



CO 

> 

4J 
•H 
CO 

C 
CU 

Q 



0) 

S-l 

too 

•H 



<X> 



C7> 

OO 



00 



00 



iooj oiano U3d saNnod 'AiisN3a Aaa 

92 




o 






CO 




• 
CO 

i-H 


00 




U-l 


CM 




60 
O 
Q 

O 

cd 
i—i 
M 


VO 




toO 


CVJ 




•H 
CO 

3 




1- 

LU 
C_> 


4J 

c 

CD 


«d" 


cc 

LU 


•U 

o 


CVJ 


•t 






1— 


3 




LU 




1— 

o 
<_> 


4J 
CO 
•H 

o 
6 




LU 




CVJ 
CVJ 


en 

1— 


co 
> 




1—1 

o 


co 




s: 






C 






CD 






T3 






^ 


o 




^l 


CVJ 




Q 



CO 



a) 

3 
toO 
•■-I 



iooj oiano *i3d saNnod 'aiisnhq Ada 



93 




o 






CO 




• 

co 

CO 

>•. 

t— 1 


CO 




<M 


CM 




e 

60 

c 

•r-l 

CO 

3 


ud 




4J 


CM 


1— 


C 




^ 


CD 




LjJ 


J-l 




o 


c 




Cd 


o 




LU 


o 




D- 


<u 




1— 


S-i 

3 




^ 


4-1 


"3- 


UJ 


CO 


CM 


1— 


•r-l 




^ 


o 




O 


s 




o 






UJ 


w 




c£ 


> 




rD 






1— 


>, 




CO 


■u 




1 — 1 


•r4 


CM 


o 


CO 


CM 




cu 

U 
Q 


O 






CM 




CU 

u 

bO 
•H 



cr> 

CO 



CO 



CO 



CO 

CO 



lood Diano cj3d sawnod 'aiisnbq Aba 



94 




CO 
CM 







si 






CO 






cfl 


VO 




>, 


CM 




Ibright fl 
). 


■* 




«■ 


CM 




bO^ 




1— 


C 




^ 


•H X! 




UJ 


CO CO 




C_) 


3 rt 




cm 






UJ 


4-1 >^ 




D_ 


0) U-J 




fl 


4-1 




I— 


C >> 


CM 


^ 


O M 


CM 


LU 


O U 




1— 


CU 




^ 


0) fa 




o 


M 




o 


3 w 

4-1 - 




UJ 


CO T3 




d; 


•H i—l 




rj 


O CU 




l— 


6 -H 




oo 


m 


o 


i — i 


• 4-) 


CM 


o 


CO ctf 

> in 




s. 






>.T3 






4-1 C 






•r-i ctj 






CO 






C 






cu 






T3 


00 




>-> 

5-1 


1 




Q 



UD 



CU 

M 
■H 

Eh 



o 



CO 
CO 



00 



00 



CM 

oo 



iooj oiano ci3d saNnod 'AiisNaa Ada 



95 



5000 i- 



2000 



en 



cr 

UJ 

I— 

00 



CO 

UJ 

a: 

Q. 

2: 
o 

O 

o 

LU 



1000 - 



5 500 



o 
o 



200 



2 

^ 



2 



I 



J 



ag 






1 



1 



2 
2 






I 



^ 



12 



ud 



z 




2; 



I 



I 

1 



i 

^ 



LIME A-, A-, 


A l A l 


A l A l 


A 2 A 2 


A 2 A 2 


A 2 A 2 


SULFATE B 1 B ] 


Dp Dp 


B 3 B 3 


B 1 B 1 


B 2 B 2 


B 3 B 3 


WATER D-j D 2 


D l D 2 


Dl D 2 


D l D 2 


D l D 2 


D l D 2 



Figure 8. Unconfined compressive strength at 7 ( l&ff&fj ) , 28 ( \//A ) and 
91 ( I ~| ) days for mixtures using Ft. Martin fl/ ash. 



96 



5000 r- 



£ 2000 



CD 



LU 

cm 



en 

LU 



£ 1000 h 

LU 

o. 
s: 
o 
c_> 



o 
o 



z 






500 I- £^ 

200 h 1^ 

II 



LIME A 1 A 1 
SULFATE B-, B 
WATER D 1 D 2 



Z 



^ 






A 



§ 



I 



z 




d 



if 

w 

mz 



U 



'/, 



9Z 



I 



I 






I 

my 

I 



B 2 B 2 
D 1 D 2 



A 1 A 1 
B 3 B 3 
D l D 2 



A 2 A 2 

B l B l 
D l D 2 



A 2 A 2 
B 2 B 2 
D 1 D 2 






it 

• : : V 



A 2 A 2 

B 3 B 3 
D 1 D 2 



Figure 9. Unconfined compressive strength at 7 ( Ex?? 
91 ( I I ) days for mixtures using Black Dog 

97 



|), 28 (EZ2) and 
fly ash. 



5000 i- 



2000 






LU 

ad 
h- 
o 

LU 



00 

LU 

en 

CL. 

o 
o 



o 
o 



1000 



500 



200 




LIME 

SULFATE 

WATER 
Figure 10. 



z 



/;/, 







4 
1 

/ 

/ 



B l B l 
D l D 2 





2? 



1/J 



J 




A l A l 
B2 B 2 

D l D 2 



A 1 A 1 
B 3 B 3 
D-, D 2 



A 2 A 2 

B l b t 
D 1 D 2 



'/?, 



A 2 A 2 
B 2 B 2 
D l D 2 




A 2 A 2 

B 3 B 3 

Dl D 2 



Unconfined compressive strength at 7 ( gj-gj-g.) ) . 28 ( JXXA ) and 

91 ( I I ) days for mixtures using Amax fly ash. 

98 



5000 i- 



2000 



OO 

o. 



CJ3 

UJ 

I— 
oo 



oo 
oo 

UJ 

on 

CL. 

o 



o 
o 



1000 - 



500 



200 



Zz 



zZ 



A 






//} 



-d 



7 



x^ 



2^ 




i 



7-y 



z 



A 



LIME 


A l A l 


A 1 A 1 


A l A l 


9 


A 2 A 2 


A 2 A 2 


SULFATE 


B l B l 


Dp DO 


B 3 B 3 


B 1 B 1 


Dp Dp 


B 3 B 3 


WATER 


D l D 2 


D-, D 2 


D l D 2 


D l D 2 


D l D 2 


D-, D 2 



Figure 11. Unconfined compressive strength at 7 ( Kw&l ) , 28 ( Y / /\ ) and 
91 ( I 1 ) days for mixtures using Albright fly ash. 

99 



5000 i— 



2000 



1000 



500 - 



200 







Tj 



LIME 

SULFATE 

WATER 



V?. 



'/, 



A 



A l A l 

B 1 B, 

D l D 2 



2 



% 



i^/y 



A. 



7 



'/7> 



2^ 



71 






A 



2 



2 



z 



A i A i 

B 2 B 2 
D 1 D 2 



A 1 A 1 
B 3 B 3 
D l D 2 



A 2 A 2 
Bl B 7 
D l D 2 





B 2 B 2 

D l D 2 



Z 



Kfe 



^ 



I 



A 2 A 2 

B 3 B 3 
D l D 2 



Figure 12. Unconfined compressive strength at 7 ( fcvxjxij ) , 28 (LZ22) and 
91 ( | 1 ) days for mixtures using Hatfield's Ferry fly ash. 

100 



3000 r- 



2500 - 



IS) 



LxJ 

an. 

V- 



(S) 

en 

UJ 

a: 

O- 

s: 
o 
o 



o 
o 



2000 - 



1500 



1000 - 





LIME 
SULFATE 



Figure 13. 



lime 



Unconfined compressive strength vs. su ]_f ate 
for Ft. Martin fly ash. 



101 



2500 



28 days 



2000 - 






CJ3 

UJ 

en 

I— 
in 



in 
in 

UJ 

cc 

Q- 

o 
o 

Q 
UJ 



o 
o 



1500 - 




1000 - 



500 - 



LIME 
SULFATE 



Figure 14, 



lime 



Unconfined compressive strength vs. — , ,. 
for Amax fly ash. 



102 



1000 



33 
O 



H 



oo 

UJ 

o 
o 



500 - 





1.0 



2.0 

LIME/SULFATE 



3.0 



4.0 



Figure 15. Optimizing the lime sulfate ratio for an 
extrudable consistency using Ft. Martin fly ash. 



103 



1000 r- 



LU 
OH 

\- 
IS) 



£ 500 
in 

LU 
OH 

a. 

o 
o 




LIME/SULFATE 

Figure 16. Optimizing the lime/sulfate ratio for an 
extrudable consistency using Amax fly ash. 



104 



2000 



cu 



UJ 

cc 



co 

UJ 



CO 

go 

LU 

a: 
ex. 

s: 
o 
o 



1500 - 



1000 




500 



7 days 



1.0 



2.0 
LIME/SULFATE 



3.0 



4.0 



Figure 17. Optimizing the lime/sulfate ratio for a slump 
consistency using Ft. Martin fly ash. 

105 



1000 




CD 

LU 
CC 

I— 
OO 

LU 



CO 
00 



D. 



O 



500 



days 



1.0 



2.0 
LIME/SULFATE 



3.0 



4.0 



Figure 18. Optimizing the lime/sulfate ratio for a slump 
consistency using Amax fly ash. 

106 



2000 i— 



in 




a. 




m 




DC 




1- 




CJJ 




2= 




LU 




OC 




1- 




</i 




LU 




> 




1— 1 




tn 




oo 




LU 




Ol 




a. 

s: 


1000 

















LU 


800 


1— 1 




u_ 




z 






-5^ 


600 



400 



200 — 




-//- 



6 8 

FLY ASH/(LIME & SULFATE) 



10 



12 



Figure 19. Unconfined compressive strength at 7 (A) and 28 (•) days 
' at varying fly ash/ (lime & sulfate) using Ft. Martin fly ash. 



107 



2000 i— 



co 



CJ3 

us 

h- 
co 

LU 



1500 



CO 
CO 

UJ 

q; 
o 

CJ 



1000 



o 

CJ> 



500 



10 



15 



20 



FLY ASH/(LIME & SULFATE) 

Figure 20. Unconfined compressive strength at 7 (d. ) and 28 (•) Days at 
varying fly ash/ (lime & sulfate) using Amax fly ash. 



108 



1000 i— 



en 



3C 
C£5 



en 



tn 

LU 

o_ 

5" 
O 

o 



800 



28 days 



600 



400 



o 
o 



200 



7 days 



4 6 

FLY ASH/(LIME & SULFATE) 



8 



10 



Figure 21. Optimizing the fly ash/ (lime + sulfate) ratio for an 
extrudable consistency using Ft. Martin fly ash. 



109 



2000 



r 



1600 — 



CO 



O 



LiJ 



in 



(S) 

UJ 

ctL 

D- 

o 
o 



o 
o 



1200 — 



800 



400 - 




4 



10 



FLY ASH/(LIME & SULFATE) 

Figure 22. Unconfined compressive strength at varying fly ash/ (lime & 
sulfate) for mixtures containing Ft. Martin (•) and Amax (£ ) 
fly ash at three-inch slump consistency. 



110 



oo 



I- 

00 



UJ 
D- 

o 
o 



o 
o 



1000 




5 10 15 

SULFATE, PERCENT 

Figure 23. Variation in strength with gypsum content 
at 7 (A) and 28 (®) days for Amax fly ash. 



Ill 



2500 



O- 



C*3 

UJ 

\- 



en 
(/) 

LU 

on 

ex. 

2: 
o 
o 



2000 



1500 




1000 - 



5 10 15 
GYPSUM, PERCENT 



20 



Figure 24. Variation in strength with gypsum content for Ft. Martin 

fly ash at 7 days (•) and 28 days (£)• 



112 




Figure 25. Scanning electron micrograph 
(SEM) of Ft. Martin fly ash - 2000X. 



113 




Figure 26. SEM of gypsum - 2000X. 



114 




Figure 27. SEM of calcitic lime - 2000X, 



115 



Ettringite 




days Yr 



12' 



16' 



20' 



24' 



28' 



Figure 28. X-ray diffraction pattern of standard mixture. 



116 




Figure 29. SEM of standard mixture - unreacted (2000X) 



117 




Figure 30. SEM of standard mixture - 7 days (2000X) . 



118 




Figure 31. SEM of standard mixture - 28 days (2000X) 



119 




Figure 32. SEM of standard mixture - unreacted (6000X) . 



120 




Figure 33. SEM of standard mixture - 7 days (6000X) 



121 




Figure 34. SEM of standard mixture - 14 days (6000X) 



122 




Figure 35. SEM of standard mixture - 28 days (6000X) 



123 




Figure 36. SEM of standard mixture - 91 days (2000X) 



124 




Figure 37. SEM of standard mixture - 9 months (1530X) 



125 




Figure 38. SEM of Calcium sulfite mixture - 91 days (2000X) 



126 




Figure 39. SEM of slump consistency mixture - 28 days (6045X) 



127 




Figure 40. SEM of extrudable consistency mixture - 7 months (2000X) . 



128 



<y 




CM 



QJ 
•U 

60 

a e 



■u 



(U 

■U N 

3 -i-l 4-» 

CO 0) i— I U 

a. B i-i ca 



W O t-J s o- 
I I I I I 

W O J s o* 



CM 



o 

CM 



v£> 



CM 



CO 

4J 

c 
o 

B 



0) 
U 

3 

4J 

•r-l 

e 

o 

3. 

0) 
■U 
CO 

•r-4 

CO 

C 

o 
o 



ct) 

3 

■U 

X 
a> 

CM 

o 

c 
u 

<D 

+J 

4J 

cd 
cu 

a. 
o 
•i-i 

■U 
O 
Ct) 

CW 
<4-l 



ccj 
u 



cu 

!-< 

3 
60 

•M 

fa 



129 




Figure 42. SEM of slump consistency mixture (9600X) 



130 




Figure 43. Acid mine drainage (W,) samples after three cycles 

of freeze- thaw. The three samples on the left were brushed: 

the three on the right were unbrushed. 



131 





(a) Standard specimen after 14 cycles of freeze- thaw. 



Figure 44. Unbrushed samples of scrubber sludge (W ft ) 

cured for 28 days. 



132 




(b) Specimens with addition of 1/2 percent calcium 
chloride after 12 cycles of freeze-thaw. 



Figure 44. Unbrushed samples of scrubber sludge (W_) 

cured for 28 days. 



133 




Figure 45. Aggregate particle subsequent to soundness test, 



134 




Figure 46. Aggregate particles after 12 cycles of freeze- thaw, 



135 




«c ; 



_ \ /. i . . ~ 



Figure 47. Concrete test specimen showing molding defects 



136 



to 
QJ 



U 



OO 



12 
10 

8 

6 

4 I 

2 




CN 

I 

o 



•1-1 

CO 



m 



S3 
O 



28 
27 
26 
25 
24 
23 
22 
21 
20 
19 
18 
17 
16 
15 



- X 



\y 



/ 



A 

/ * 28 day 



\ 



7 day 



6 7 
CEMENT FACTOR 



Figure 48. Variation in compressive strength 
with slump and cement factor. 



137 



eg 



•H 
CO 



H 
O 

H 
CO 



CO 
CO 



O 
O 

















«. — # 7 day strength 




36 


letters identify gradations 




34 






C< 






>C 


32 














30 






B( 








28 












► B 


26 






Ct 


r*~-~~ 


— - -"* ' 


> C 


24 






B< 






► A 


22 


- 




A 


^ 


"*«s» 


► B 


20 








A 












/ / 






> A 


18 






/ / 
/ / 








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5 6 7 

CEMENT FACTOR, bags /yd 3 

Figure 49. Variation in compressive strength 
with aggregate gradation for w/c of 0.51 



138 





30 




28 


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» t 28 day strength 

•- •• 7 day strength 

letters identify gradations 




CEMENT FACTOR, bags/yd 

Figure 50. Variation in compressive strength 
with aggregate gradation for w/c of 0.68. 



139 




I 



\ 



Figure 51. Typical surface cracks on freeze- thaw 
concrete specimen. 



140 




Figure 52. Freeze-thaw concrete specimens after 

103 cycles. 



141 






4J. ' t 






''"'/- * ' '■■£ -* > ■ k'jf :: • • '. <■ 

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Figure 53. Close-up view of interior surface of 
freeze-thaw concrete specimen. 



142 



Table 1. Material sources and designations. 



A - LIME 

A, National Gypsum Company 

#26 Chemical Hydrated Lime 

Manufactured at Belief onte, Pennsylvania 

A_ Warner Company 

"Limoid" - Dolomitic Monohydrated Lime 
Manufactured at Devault, Pennsylvania 

A~ Foote Mineral Company 

Foote High Calcium Lime 
Manufactured at Knoxville, Tennessee 

A, Pfizer, Inc. 

Nelco® Dolomitic Chemical Hydrated Lime 
Manufactured at Canaan, Connecticut 

B - CALCIUM SULFATE 

B- Fisher Chemical Company 

Finely precipitated gypsum 

B 9 U. S. Gypsum Company 

Terra Alba #1 
Manufactured at Alabaster, Michigan 

B~ City Chemical Company 

Calcium sulfite dihydrate 

B, J. T. Baker Chemical Company 
Calcium sulfate, anhydrous powder 

C - FLY ASH 

C, Fort Martin Power Station 

C_ Black Dog Power Station 

C„ Amax Fly Ash Company 

Mitchell Power Station 

C, Albright Power Station 

C, Hatfield's Ferry Power Station 

D - WATER CONTENT 

D Compactible Consistency 

D Extrudable 

e 

D Three- inch slump 

s 

143 



Table 2. Chemical and physical analysis of lime. 



CHEMICAL PROPERTIES 



LIME 



A l *2 3 4 

National Gypsum Warner Foote Pfizer 



CaO, percent 
MgO , percent 
SiO„, percent 
Fe-CL, percent 
Al.Oo, percent 



73.5 


46.4 


72.3 


44.8 


0.7 


33.4 


0.4 


26.2 


1.1 


2.2 


0.05 


1.4 


0.2 


0.3 


0.2 


0.5 


0.3 


0.5 


0.5 


0.2 



PHYSICAL PROPERTIES 



Loss on Ignition, 110°C, percent 
Loss on Ignition, 950°C, percent 

Surface area, cm /gm 

/ 3 
Density, gm/cm 

Sieve Analysis: 
Passing #100, percent 
Passing #200, percent 
Passing #325, percent 



0.9 
24.0 
29,500 

2.3 



0.5 0.7 0.4 

17.4 24.9 38.0 

21,000 31,000 19,000 

2.6 2.3 2.6 



100 


92 


100 


90 


99 


75 


99 


72 


95 


62 


97 


55 



144 



Table 3. Analysis of fly ash. 



'1 u 2 °3 ^4 °5 
Ft. Martin Black Dog Amax Albright Hatfield's Fy. 















A1 ? 0„, percent 


23.8 


21.1 


23.6 


27.4 


24.6 


Si0 2 , percent 


47.8 


39.5 


45.6 


53.6 


48.5 


Fe.O,,, percent 


17.2 


7.4 


14.3 


10.4 


14.3 


CaO, percent 


3.8 


21.9 


6.0 


1.3 


4.1 


MgO , percent 


1.2 


5.9 


1.2 


0.7 


1.1 


K 2 0, percent 


2.3 


0.5 


1.8 


2.1 


1.7 


Na 2 0, percent 


0.8 


0.6 


1.0 


0.3 


0.7 


S0„, percent 


0.1 


1.4 


0.2 


< 0.1 


< 0.1 


P-0 5 , percent 


0,5 


0.4 


0.7 


0.4 


0.3 



Loss on Ignition, 
110°C, percent 

Loss on Ignition, 
950°C, percent 

PH 

Specific Gravity 

Blaine Fineness, 
cm^/gm 

Surface Area, 
cm^/ cm3 

Residue on #325-wet, 
percent 

Sieve analysis, 
percent 

Retained on #4 
Retained on #8 
Retained on #20 
Retained on #50 
Retained on #100 
Retained on #200 
Passing #200 



0.1 



0.7 



6.4 



0.1 



0.5 



1.2 


1.7 


5.7 


2.0 


3.1 


8.9 




10.7 


10.9 


10.5 


2.39 


2.28 


2.43 


2.12 


2.34 


2404 


4210 


4339 


1980 


2456 


5746 


9599 


10,544 


4198 


5746 


15.9 




10.4 


18.9 


22.0 



< 0.1 


< 0.1 


< 0.1 


< 0.1 


< 0.1 


< 0.1 


< 0.1 


< 0.1 


< 0.1 


< 0.1 


0.2 


0.6 


< 0.1 


< 0.1 


< 0.1 


0.7 


6.2 


0.8 


0.4 


0.5 


10.8 


5.4 


6.3 


4.7 


3.8 


30.4 


14.6 


51.3 


21.9 


21.6 


57.9 


73.2 


41.6 


73.0 


74.1 



145 



Table 4. Standardization of Harvard miniature compactor. 



Wet Density, lb/ft 



3a 



y Standard Apparatus Harvard Compactor 



25 
30 
35 

40 



103.6 



99.1 
100.8 
101.4 
103.3 



a 1 lb/ft 3 =16.0 kg/m 3 . 



Table 5. Calibration of extruder. 



Setting 



Rate of Extrusion (gm/min) 



2 
3 
4 

5 



260 (34.6 lbs/hr) 

445 (58.5 lbs/hr) 

620 (82.1 lbs/hr) 

725 (95.8 lbs/hr) 



Table 6. Calibration of miniaturized slump cone. 



Slump, inches 



Standard Cone 



Miniature Cone 



5 
3 

1% 



2% 
1% 



146 



Table 7. Optimum moisture content for fly ash-lime-sulfate mixtures. 



Fly Ash Source 



Optimum Moisture Content, percent 



C, Fort Martin 



C_ Black Dog 



C. Amax 



C, Albright 

C- Hatfield's Ferry 



20.2 
22.7 
24.2 
20.0 
19.5 



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3. 

Table 13. Comparison of means by least significant difference , 



Material 




, . b 
Ranking 










1 


2 


3 


4 


5 








7 -DAY 


COMPACTIBLE 






Lime 

(LSD = 0.016) 


A 2 
2.573 


A l 
2.546 










Sulfate 

(LSD = 0.019) 


B 2 
2.596 


B l 
2.588 


B 3 
2.496 

C 2 C 5 
2.596 2.552 

COMPACTIBLE 


C 4 
2.250 




Fly Ash 

(LSD = 0.025) 


U 3 
2.701 


C l 
2.700 








28-DAY 




Lime 

(LSD = 0.020) 


A l 
3.295 


A 2 
3.274 










Sulfate 

(LSD = 0.025) 


B l 
3.290 


B 2 

3.282 


B 3 
3.281 


C 5 
3.300 


C 4 
3.082 




Fly Ash 

(LSD = 0.032) 


C l 
3.392 


C 3 
3.345 


C 2 
3.302 














a. Values reported are logarithms of the means. 

b. Underlined materials are not significantly different from each other. 



153 



Table 14. Comparison of means for different ashes* 



Fly Ash 



Ranking ° 
2 



7 DAYS - COMPACTIBLE 



1 m : . 

Lime 

(LSD = 0>052) 

Sulfate 

(LSD = 0*064) 



2 

2.761 

B, 



1 
2.638 

B„ 



2.740 



2.722 



B 3 
2.638 



Lime 

(LSD = 0.044) 

Sulfate 

(LSD = 0.054) 



1 
2.659 

B„ 



2 

2.533 

B, 



2.642 



2.629 



B 3 
2.517 



Lime 

(LSD = 0.028) 



Sulfate 

(LSD = 0.035) 



2.715 
B„ 



2.744 



2.687 
B, 



2.723 



B 3 
2.635 



Lime 

(LSD = 0.020) 

Sulfate 
(LSD = 0.02 



2 
2.261 

B„ 



2.278 



1 
2.239 

B. 



2.267 



B 3 
2.206 



154 



Table 14 (continued) 



Fly Ash 



Ranking" 3 
2 



Lime 

(LSD = 0.035) 

Sulfate 

(LSD = 0.043) 



2 
2.597 

B 



1 
2.506 

B 



2.594 



2.579 



B 3 
2.482 



28 DAYS - COMPACTIBLE 



Lime 

(LSD = 0.083) 



Sulfate 

(LSD = 0.102) 



3.411 
B„ 



3.416 



3.373 
B, 



3.390 



3.371 



Lime 

(LSD = 0.056) 

Sulfate 

(LSD = 0.069) 



1 
3.336 

B„ 



3.310 



2 
3.267 

B„ 



3.308 



3.287 



Lime 

(LSD = 0.025) 

Sulfate 



1 
3.387 

B 3 

3.360 



2 

3.304 

B l 
3.354 



B 2 
3.322 



155 



Table 14 (continued) 



Fly Ash 



Ranking 
2 



28 DAYS - COMPACTIBLE 



Lime 

(LSD = 0.030) 



Sulfate 

(LSD = 0.036) 



3.097 
B, 



3.122 



3.068 
Bo 



3.099 



B 3 
3.026 



Lime 

(LSD = 0.027) 



Sulfate 

(LSD = 0.033) 



3.310 
B„ 



3.310 



3.291 
B„ 



3.297 



3.294 



a. Values reported are the logarithms of the means. 

b. Underlined materials are not significantly different from each other, 

c. Not significantly different according to analysis of variance. 



156 



Table 15. Variation in lime/sulfate ratio for Ft. Martin fly ash. 



Lime a , 


b 
Gypsum , 

percent 


Consistency 


Dry Density, 
lb/ft3 d " 


Unconfined 
Strength, 


Compressive 
lb/in2 e 


percent 


7 days 


28 days 





20 


D 
c 


82.8 


40 


45 


2 


18 


D 
c 


87.1 


570 


855 


4 


16 


D 
c 


88.6 


570 


1590 


6 


14 


D 
c 


88.2 


575 


2245 


8 


12 


D 
c 


88.5 


575 


2505 


10 


10 


D 
c 


88.5 


610 


2675 


12 


8 


D 
c 




400 


1905 


4 


16 


D 

e 




115 


95 


8 


12 


D 

e 




95 


1050 


12 


8 


D 

e 




85 


1235 


16 


4 


D 
e 




130 


1060 


8 


12 


D 
s 




155 


1835 


10 


10 


D 
s 




160 


1300 


12 


8 


D 
s 




135 


2180 


16 


4 


D 
s 




120 


1005 



a. A, - calcitic lime. 

b. B - ground gypsum. 

c. D - compactible; D - extrudable; D - three-inch slump. 

d. 1 lb/ft 3 = 16.0 kg/m 3 . 

e. 1 lb/in 2 =6.89 kN/m 2 . 



157 



Table 16. Variation in lime/sulfate ratio for Amax fly ash. 



Lime , 


b 
Gypsum , 

percent 


c 
Consistency 


Dry Density, 
lb/ft3 d 


Unconfined 
Strength, 


Compressive 
, lb/in2e 


percent 


7 days 


28 days 





20 


D 
c 


84.6 


95 


125 


2 


18 


D 
c 


84.7 


440 


735 


4 


16 


D 
c 


84.6 


575 


1205 


6 


14 


D 
c 


85.2 


620 


1775 


8 


12 


D 
c 


79.3 


650 


1995 


10 


10 


D 
c 


89.1 


620 


2460 


12 


8 


D 
c 


87.3 


570 


1905 





20 f 


D 
e 




55 


70 


4 


16 f 


D 
e 




80 


115 


8 


12 f 


D 
e 




85 


145 


12 


8 f 


D 
e 




90 


935 


16 


4 f 


D 
e 




95 


695 


8 


12 


D 
s 




105 


785 


10 


10 


D 
s 




90 


820 


12 


8 


D 
s 




85 


1030 


16 


4 


D 
s 




80 


770 



a. A - dolomitic lime. 

b. B_ - ground gypsum. 

c. D - compactible; D - extrudable; D - three- inch slump. 

d. 1 lb/ft 3 =16.0 kg/m 3 . 

e. 1 lb/in 2 = 6.89 kN/m 2 . 



f. B, - precipitated gypsum. 



158 



Table 17. Density and unconf ined compressive strength at various 
fly ash/(lime + sulfate) ratios using Ft. Martin fly ash. 



Lime , 
percent 


b 
Gypsum , 

percent 


Fly Ash, 
percent 


c 
Consistency 


Dry 
Density, 
lb/f t 3 d 


Unconf ined 
Strength, 
7 days 


Compressive 
, lb/in2 e 
28 days 


5.7 


11.3 


83 


D 
c 


87.9 


535 


2045 


4.7 


9.3 


86 


D 
c 


88.1 


545 


2065 


3.7 


7.3 


89 


D 
c 


88.7 


570 


1665 


2.7 


5.3 


92 


D 
c 


88.3 


600 


1130 


6.0 


4.0 


90 


D 
e 




175 


570 


9.0 


6.0 


85 


D 

e 




110 


745 


18.0 


12.0 


70 


D 

e 




135 


760 


24.0 


16.0 


60 


D 
e 




105 


715 


4.0 f 


6.0 


90 


D 
s 




170 


480 


8.0 f 


12.0 


80 


D 
s 




155 


1840 


12. f 


18.0 


70 


D 
s 




155 


1705 


16. f 


24.0 


60 


D 
s 




115 


1090 



a. A 1 - calcitic lime. 

b. B - ground gypsum. 

c. D^ - compactible; D - extrudable. 

c e 

d. 1 lb/ft 3 =16.0 kg/m 3 . 

e. 1 lb/in 2 =6.89 kN/m 2 . 

f. A» - dolomitic lime. 



159 



Table 18. Density and unconfined compressive strength at various 
fly ash/ (lime + sulfate) ratios using Amax fly ash. 



a _ b „•••»!_ Dry Unconfined Compressive 

Lime , Gypsum , Fly Ash, _ . c * \. 9e 

' Jr " J ' Consistency Density, Strength, l b/in* e 

lb/ft3d 7 days 28 days 



percent percent percent 



6.8 


10.2 


83 


5.6 


8.4 


86 


4.4 


6.6 


89 


3.2 


4.8 


92 


2.0 


3.0 


95 


6.0 


4.0 


90 


12.0 


8.0 


80 


18.0 


12.0 


70 


24.0 


16.0 


60 



85.6 
87.0 
85.7 
85.3 
86.9 



D 



D 



505 
570 
530 
620 
425 

90 

85 

105 

50 



1955 
1770 
1480 
1130 
740 

480 

1030 

640 

305 



a. A„ - dolomitic lime. 

b. B„ - ground gypsum. 

c. D - compactible, D - three- inch slump. 



d. 1 lb/ft 3 =16.0 kg/m 3 . 

e. 1 lb/in 2 =6.89 kN/m 2 . 



160 



Table 19. Density and strength of compacted specimens 
with increasing sulfate content. 



Lime, 


Sulfate, 
percent 


Fly Ash, 
percent 


Dry Density, 
lb/ft3 a 


Unconfined 
Strength, 


Compressive 
, lb/in2 b 


percent 


7 days 


28 days 


A 2 


B 2 


C 3 








3.4 





96.6 


85.3 


420 


690 


3.2 


4.8 


92.0 


85.7 


620 


1130 


3.2 


6.2 


90.7 


86.5 


685 


1105 


3.1 


7.3 


89.5 


86.2 


680 


1035 


3.1 


8.4 


88.5 


86.2 


730 


1090 


3.0 


9.9 


87.1 


85.7 


680 


1075 


2.9 


13.0 


84.1 


86.0 


360 


900 


2.8 


16.6 


80.6 


86.1 


400 


865 


A l 


B l 


C l 








4.7 





95.3 


89.4 


225 


360 


4.7 


2.3 


93 


88.2 


625 


1190 


4.7 


4.3 


91 


88.6 


575 


2125 


4.7 


6.3 


89 


88.9 


535 


2140 


4.7 


9.3 


86 


87.9 


540 


2070 


4.7 


12.3 


83 


86.6 


485 


1580 


4.7 


18.3 


77 


85.0 


460 


1435 



a. 1 lb/ft 3 =16.0 kg/m 3 . 

b. 1 lb/in 2 =6.89 kN/m 2 . 



161 



Table 20. Unconfined compressive strength of lime-fly ash and 
lime-sulfate-fly ash mixtures. 



Lime 


Sulfate 


Fly 


Ash 


Dry 
Density, 
lb/f t 3 a 


Unconfined 


Compressive 
lb/in2b 


Strength 




7 days 


28 days 


91 days 


A 2 = 5.6% 







C 3 = 


94.4% 


84.0 


400 


645 


915 


A 2 = 5.6% 


B 2 


= 8.47= 


C 3 = 


87% 


87.1 


570 


1770. 


- 


^ = 4% 







C 5 = 


96% 


81.0 


205 


565 


940 


A 2 = 4% 


\ 


= 4 


C 5 = 


92% 


84.4 


340 


1145 


1300 


A 2 = 10% 







C 3 = 


90% 


77.7 


90 C 


205° 


580 C 


A 2 = 107c 


B 2 


= 10% 


C 3 = 


80% 




90° 


820° 


- 



a. 1 lb/ft 3 =16.0 kg/m 3 . 

b. 1 lb/in 2 =6.89 kN/m 2 . 

c. 3-inch slump consistency. 



162 



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CM CM rH rH r-l 



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164 



Table 23. Unconfined compressive strength of mixtures 
prepared using anhydrous calcium sulfate. 















Unconfined 


Compressive 




Sulfate 




Fly 


Ash 


Strength 


, lb/in2 b 


Lime 


7 days 


28 days 


A 2 - 4.4% 


B 4 


- 6.6% 




C 3" 


89% 


715 


1350 


A 2 - 4.4% 


B 2 


- 6.6% 




C 3" 


89% 


530 


1480 


A 2 - 3.2% 


B 4 


- 4.8% 




C 3" 


92% 


615 


1145 


A 2 - 3.2% 


B 2 


- 4.8% 




C 3" 


92% 


620 


1130 


A x - 3.7% 


B 4 


- 7.3% 




C l" 


89% 


1110 


2165 


A x - 3.7% 


B 2 


- 7.3% 




C l" 


89% 


570 


1665 


A x - 12% 


B 4 


- 8% 




C 4" 


80% 


375 


1865 


A x - 12% 


B l 


or B 2 - 


8% 


C 4- 


80% 


180 


~ 1200 


A x - 12% 


B 4 


- 8% 




C 4- 


80% 


75 c 


340 c 


A x - 12% 


B l 


or B 2 - 


8% 


C 4" 


80% 


~ 90 c 


~ 475 c 


A x - 12% 


B 4 


- 8% 




S- 


80% 


705 


2055 


A x - 12% 


B l 


or B 2 - 


8% 


C 5" 


80% 


~ 350 


~ 2030 


A x - 4% 


B 4 


- 6% 




C l" 


90% 


210 C 


325 C 


A ± - 4% 


B 2 


- 6% 




C l" 


90% 


170 C 


480 c 



a. B, - anhydrous calcium sulfate. 

b. 1 lb/in 2 =6.89 kN/m 2 . 

c. 3-inch slump consistency. 



165 



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172 



Table 31. Waste sulfate analysis . 





W l 


W 2 


W 
3 


W 4 


w 5 


W 6 


W 7 


W 
w 8 


Free Water, percent 


57 


53 


94 


41 





24 


63 


53 


Combined Water, percent 


91 


80 


98 


60 


15 


40 


69 


52 


SiC^, percent 


1 


2 


1 


17 


12 


19 


1 


2 


Feo03 + AI2O3, percent 


7 


9 


1 


4 


2 


18 


9 


1 


CaO, percent 


7 


15 


3 


20 


54 


28 


16 


32 


S0„, percent 


4 


13 


2 


13 


43 


5 


1 


4 



a. ASTM Method C471-66, "Chemical Analysis of Gypsum and Gypsum Products." 



173 



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> 


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176 



Table 35. Formulations evaluated for engineering properties. 



Formulation 



Lime 



Fly Ash 



Sulfate 



Water 



4.7% A, 



86% C. 



9.37o B, 



(calcitic) 


(Ft. Martin) 


(gypsum) 


5% A x 


80% C. 


15% W 2 


(calcitic) 


(Ft. Martin) 


(Acid Mine Drain- 
age Sludge) 


4% A 2 


85% C 3 


11% w 5 


(dolomitic) 


(Amax) 


(HF By-product) 


5% A x 


76% C 


19% W, 
6 


(calcitic) 


(Ft. Martin) 


(Scrubber Sludge) 


5% A 


83% C 1 


12% W, 
4 


(calcitic) 


(Ft. Martin) 


(Titangypsum) 


5.6% k ± 


61.6% C 3 


32.8% W g 


(calcitic) 


(Amax) 


(Scrubber Sludge) 



19.5% 



5% 



24% 



11% 



5% 



2% 



a. Percent of wet sludge by weight. 

b. Additional water needed to obtain optimum moisture content, 



177 



Table 36. Engineering tests performed on selected formulations. 

Sample Curing Age (Days) 
Test 7 15 28 90 

Compressive Strength x x x 

Split Tensile Strength x x x 

Freeze-Thaw x 

Wet-Dry x 

CBR (California Bearing Ratio) x x 

Permeability x x 

Leachability x x 



178 



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r-l 


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182 











£ 


§ 




£ 










CO 


cO 




CO 








X! 


X! 




X! 








H 


H 




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CD 4-t 


» 


1 




1 


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Cu co 


CD 


CD 




CD 


J-l 




>> CD 


N 


N 




N 


Q 




H H 


CD 


CD 




CD 


1 






CD 


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J-l 


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fa 


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d *>4-i 
















4-» CD d 














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CO 60 CD 


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CD 

43 














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1 




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n 


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X! 


Cu CD 












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CD -H 


60 


CO o 












CL J-l 


d 


CO >> 












CO 3 


CD 


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4J 


CD CN 


o 


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CN 


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VO 


>> 




CO 


CO 


CN 




CM 


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>> CO 


CD 


d j-i 












U T3 


> 


U CD 












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g 00 


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cd d 














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CD CD 












• 


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r-l r-4 












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CD 


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d 


CN 


1 


1 




1 


rH 


Xl 


•i-i 


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CO 


m 


CD 












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d 
o 
o 
d 


brush 
after 






















CD 














U 


( 




d 








d 






o 






CN 


4-t 






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rH 00 CO 


i— 1 00 COrH 


X 


rH 00 CO rH CO CO i 




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u 


< IS CJ J-l 


<J IS CJ CJ 


•H 


< IS CJ S-i 


< IS CJ 




CO 


CD CD 


CD CD 


CO 


S 


CD CD 






r-H 


Xi 60 


6-2 Xl 60 


CJ 




Xl 6C 






d 


X "d 


B~2 6-2 X "d 


S-S 5^2 


o. 


6-2 6-2 6-2 XI T3 


6-2 6-2 




a 


zz 


vO \D ? 


vO vO 6-2 


B 


r-*. vo r~~ d d 


vO vO ! 




• B^ • J-l rH 


•6-2 • CM 


d 


• • • J-l rH 


• 6^ • 




o 


CJ CO 


lO CO rH o CO 


UO CO rH -^ 


rH 


cj-\ cm I s * o co 


LO CO rH 






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n 


CO 


CO vO CO 


CO vO rH 


CO 


rH r-. CO 


CO v£> 



CM 

B 



vO 



CM 

d 



60 

d 

•r4 
J-l 

d 

CJ 
60 

d 

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d 

Q 



CO Xi 



183 



Table 42. Leachate analysis. 











Alkalinity, PPm 


Hardne; 


ss, ppm 


Sulfate, 


Al, 


Sample 




PH 


npii 


llrpH 


Ca 2+ 


Total 


ppm 


ppm 


Standard Mix. 


Initial 


12.3 


1171 


1277 


994 


1015 


3075 




- 7 


days 


Final 


11.2 


151 


174 


995 


1025 


1515 




—28 


days 


Initial 


9.6 


32 


76 


1112 


1127 


6007 








Final 


9.5 


17 


35 


1111 


1113 


1790 




W 2 - 7 


days 


Initial 


12.4 


1449 


1634 


104 


133 


30 








Final 


10.9 


798 


832 


760 


770 







- 28 


days 


Initial 


12.2 


1228 


1399 


183 


207 











Final 


12.0 


532 


567 


427 


460 







W 4 - 7 


days 


Initial 


11.9 


1624 


1740 


2444 


2320 


2780 


0.2 


- 28 


days 


Initial 


10.7 


104 


188 


518 


608 


2560 


0.2 


W 5 - 7 


days 


Initial 


11.2 


225 


287 


1469 


1540 


5147 








Final 


10.7 


67 


83 


750 


753 


953 




- 28 


days 


Initial 


8.1 


8 


40 


1233 


1460 


4520 








Final 


8.0 


7 


25 


969 


1100 


1727 




W 6 - 7 


days 


Initial 


12.7 


3405 


3507 


545 


580 











Final 


11.7 


323 


359 


299 


300 







- 28 


days 


Initial 


12.6 


2280 


2473 


73 


93 


13 








Final 


12.1 


627 


740 


720 


793 







W 8 - 7 


days 


Initial 


10.5 


1866 


1952 


2372 


2594 


2520 


0.2 


- 28 


days 


Initial 


11.7 


152 


250 


650 


774 


585 


7.5 


Wg- 28 


days 


5,900 ml 


11.2 


360 


520 


68 


80 


240 


17.0 






15,950 ml 


10.4 


12 


40 


164 


188 


90 








27,000 ml 


10.5 


40 


48 


132 


216 


30 








4,200 ml 


11.7 


660 


792 


128 


216 


660 


10.2 






8,500 ml 


10.7 


48 


48 


216 


224 


70 








17,350 ml 


10.8 


56 


40 


152 


260 


20 








6,350 ml 


11.7 


640 


756 


178 


282 


510 


5.0 






15,500 ml 


10.5 


44 


40 


188 


184 


100 








27,500 ml 


10.6 


48 


20 


144 


204 


40 





184 



Table 43. Sulfate soundness test results. 







Grading of 


Weight of 


Amount 


Weighted 


Sieve 


Size 


Original 
Sample, 


Test Frac- 
tions before 


Passing 
Sieve Used 


Average 
(corrected 






Passing 


Retained 


Percent 


Test, g. 


to Deter- 


percentage 




on 






mine Loss 


loss) 










Weight , g . Percent 




No. 100 




6 


100.3 


4.5 


- 


50 


No. 100 


14 


100.5 


40.2 


- 


30 


50 


21 


101.6 


29.4 28.9 


6.07 


16 


30 


21 


101.0 


35.0 34.6 


7.27 


8 


16 


18 


108.1 


42.1 38.9 


7.00 


44 


8 


17 


100.0 


37.4 37.4 


6.36 


3/8 


4 
Totals 


3 


0.0 


0.0 


1.12 




100 


611.5 




27.82 



Table 44. Freeze-thaw soundness test results 



Sample 1 Sample 2 Average of Samples 



Initial weight, g. 300 300 300 

Retained weight, g. 

Weight loss, percent 100 100 100 



185 



Table 45. Concrete mixtures containing cast aggregate . 



Cement Factors, bags per cubic yards 
Aggregation z a — E ■* 

Gradation 5 6 7 8 

A 1 1,3, BF 1 

B 1 1,1F,2, 1,B 

3,BF 

C 1,2 1,2,3, 1 

B,BF 



Table 46. Concrete mixtures containing extruded aggregate . 

. ... Cement Factors, bags per cubic yards 
Aggregation * a — c * 

Gradation 5 6 7 8 



A 1 

B 1 

C 1,2 



a. Series are described as follows: 

1 Coarse aggregate and sand (ASTM C-33) blended 50-50 percent by 
weight, SSD. 

IF Same as series 1 but with 10 percent by weight fly ash replacement 
of the cement. 

B Same as series 1 but with 50 percent by weight synthetic fine 
aggregate replacement of the sand. 

BF Same as series B but with 10 percent by weight fly ash replacement- 
ment of the cement. 

2 Same as series 1, but the coarse aggregates were vacuum saturated 
with water prior to mixing. 

3 All synthetic aggregate (SSD) with blends of coarse and fine 
gradation of 55 to 45, 50 to 50, and 45 to 55 percents for 
gradations A, B and C, respectively. 

186 



Table 47. Flow test of fine aggregate mixtures. 



Mixture 



Change in Diameter, percent 



Initial 



Delayed 



Remixed 



Aggregate only 
Aggregate and Cement 



25 
59 



40 
15 



106 
51 



187 





Table 48 


Concrete evaluation test 


results . 




(1) 


(2) 


(3) 


(4) 


(5) 


(6) (6) 


(7) 






Slump, 


Air 
content, 


Compressive Strength, 
lb/in 2c 


Tensile 

Strength, 

lb/in 2C 








Mix No. 


Water /Cement 


inches 


percent 


7 -day 


2 8- day 


28-day 


Cast Aggregate Mixture, 


s 










AWM-6 


0.51 





NT 


938 


1106 


275 


AWM-7 


0.51 


3 


5.0 


1925 


2145 


455 


AWM-8 


0.51 


9 


NT 


1870 


2270 


354 


BWM-7 


0.51 


2 


8.0 


2093 


2518 


409 


BWM-7-2 


0.51 


2 


8.2 


2547 


3223 


NT 


BWM-8 


0.51 


8 


NT 


2184 


2801 


332 


BWM-7 


0.51 


1 


8.0 


2600 


3346 


388 


BWM-8 


0.51 


5 


7.4 


2729 


3403 


374 


BSM-7 


0.51 


7 


10.0 


2267 


2988 


NT 


CSM-7 


0.51 


7 


10.0 


1974 


2374 


320 


AWM-5 


0.68 


7 


11.0 


1289 


2038 


294 


BWM-5 


0.68 


6 


NT 


1583 


2299 


292 


BWM-7 


0.68 


10 


NT 


1180 


NT 


NT 


CWM-5 


0.68 


3 


7.8 


1928 


2822 


NT 


CWM-5-2 


0.68 


2 


8.2 


2029 


2567 


358 


CWM-6 


0.68 


8 


NT 


1586 


2033 


351 


CWM-7 


0.68 


10 


NT 


1708 


2358 


NT 


CWM-8 


0.68 


12 


NT 


1570 


1861 


325 


CSM-5 


0.68 


7 


NT 


NT 


NT 


NT 


CSM-7-2 


0.68 


10 


NT 


1385 


2485 


264 


AWL- 7 


0.85 


3 


4.5 


1212 


2185 


NT 


BWL-7 


0.94 


5 


4.5 


960 


1807 


NT 


CWL-7 


0.90 


3 


4.8 


1695 


3095 


NT 


AWM-8 


0.46 


5 


5.8 


2540 


3198 


NT 


BWM-7 


0.90 


12 


NT 


1607 


2818 


NT 


CWM-7 


0.70 


6 


9.5 


740 


1429 


NT 


AWM-7BF 


0.70 


5 


4.0 


2140 


2327 


325 


BWM-7BF 


0.70 


3 


4.2 


1783 


2696 


331 


BWM-7BF- 


2 0.70 


10 


NT 


1093 


1806 


NT 


CWM- 7BF 


0.70 


Varied 


NT 


1528 


2384 


NT 


CWM-7B 


0.70 


Varied 


6.6 


1630 


2409 


349 


BWM-8B 


0.51 





7.2 


2076 


NT 


343 


BWM-7F 


0.51 


2 


6.6 


2329 


3370 


334 


Extruded 


Aggregate 












AWM-5E 


0.70 


2 


9.4 


1117 


1364 


110 


BWM-5E 


0.68 


3 


8.8 


1110 


1402 


202 


CWM-5E 


0.68 


4 


10.3 


997 


1397 


198 


CSM-5E 


0.68 


2 


7.0 


1224 


1680 


201 


BWM-7E 


0.51 


7 


9.2 


1167 


1659 


216 


AWM-6E1 


0.71 


6 


10.8 


1135 


1481 


198 


AWM-6E2 


0.67 


6 


8.2 


1275 


1584 


224 


AWM-6E3 


0.67 


5 


8.4 


,.015 


1389 


195 


AWM-6E4 


0.67 


10 


8.2 


911 


1207 


188 



a. The symbol NT refers to data which were not tested. Freeze-thaw 
specimens were molded from some mixtures listed which precluded 
molding a full complement of cylinders. 

b. 1 in = 2.54 cm. 

c. 1 lb/in 2 =6.89 kN/m 2 . 

188 



Table 49. Statistical analysis of concrete strength properties. 



Mixture 
Number 


Mean Strength, 
lb/in2 a 


Standard Deviation, 
lb/in2 a 


Coefficient of 
Variation, percent 


Series 
AWM-6E 


Compression 
7-day 28-day 


Tension 
28-day 


Compression 
7-day 28-day 


Tension 
28-day 


Compression 
7-day 28-day 


Tension 
28-day 


(1) 


(2) 


(3) 


(4) 


(5) 


(6) 


(7) 


(8) 


(9) 


(10) 


1 


1136 


1481 


198 


14 


214 


38 


1.3 


14.4 


19.0 


2 


1275 


1585 


224 


37 


135 


21 


2.9 


8.5 


9.2 


3 


1015 


1389 


195 


50 


95 


36 


4.9 


6.9 


18.2 


1,2 and 
3 


1142 


1486 


206 


130 


98 


16 


11.4 


6.6 


7.8 



a. 



1 lb/in 2 =6.89 kN/m 2 . 



189 



Table 50. Freeze-thaw test results for concrete, 



Beam 
Specimen 



Age at Start 
of Test, days 



Number 
of Cycles 



Modulus Ratio 



Number of 

Cycles to 

Termination 



Screening Test 



BWM-7-2 


7 


50 


0.97 


BWM-7-2 


28 


50 


0.96 


BSM-7 


7 


50 


0.65 


BSM-7 


28 


15 


0.33 


CWM-7-2 


7 


50 


1.00 


CWM-7-2 


28 


50 


1.00 


CSM-7-2 


7 


50 


0.65 


CSM-7-7 


28 


50 


0.79 


CWM-5 


7 


50 


1.00 


CWM-5 


28 


50 


1.00 


CSM-5 


7 


50 


0.68 


CSM-5 


38 


40 


0.56 


CSM-5E 


28 


50 


1.00 


CSM-5E-1 


28 


50 


1.00 


CSM-5E-2 


28 


50 
Follow-up Test 


0.95 



CWM-7-2 u 

CWM-5 b 

BWM-7-2 b 

CWM-5E 

CSM-5E-1 

CSM-5E-2 



28 
28 
28 
28 
28 
28 



31 
31 
31 
46 
46 
46 



0.90 

0.71 

0.97 

0.10 
Crumbled 
Crumbled 



50 
50 
50 
15 
50 
50 
50 
50 
50 
50 
50 
40 
50 
50 
50 



53 

53 
53 
46 
46 
46 



a. Measured from an initial value of unity at the beginning of both 
screening and follow-up tests. 

b. Freezing water contained 2 percent sodium chloride by weight. 



190 



6(J. S. GOVERNMENT PRINTING OFFICEi 19 7 6-211-173/633 








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